Composition and method of manufacturing calcium magnesium sulfonate greases without a conventional non-aqueous converting agent

ABSTRACT

An overbased calcium magnesium sulfonate grease composition and method of making such grease without using any conventional non-aqueous converting agents, such as hexylene glycol, as a pre-conversion ingredient. The addition of magnesium sulfonate as an ingredient prior to conversion appears to act as a new, non-conventional converting agent, resulting in greases with improved thickener yield and excellent dropping point.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. provisional patentapplication No. 62/338,193 filed May 18, 2016.

BACKGROUND OF THE INVENTION 1. Field of the Invention

This invention relates to overbased calcium magnesium sulfonate greasesmade without any conventional non-aqueous converting agents to produce asulfonate-based grease with a high dropping point and good thickeneryield. This invention also relates to such greases made without aconvention non-aqueous converting agent in combination with one or moreof the following methods or ingredients: (1) the addition of calciumhydroxyapatite and/or added crystalline calcium carbonate ascalcium-containing bases for reacting with complexing acids; (2) theaddition of an alkali metal hydroxide; (3) the delayed addition ofmagnesium sulfonate; (4) a split addition of magnesium sulfonate; or (5)a delay between the addition of a facilitating acid and the nextsubsequent ingredient.

2. Description of Related Art

Overbased calcium sulfonate greases have been an established greasecategory for many years. One known process for making such greases is atwo-step process involving the steps of “promotion” and “conversion.”Typically the first step (“promotion”) is to react a stoichiometricexcess amount of calcium oxide (CaO) or calcium hydroxide (Ca(OH)₂) asthe base source with an alkyl benzene sulfonic acid, carbon dioxide(CO₂), and with other components to produce an oil-soluble overbasedcalcium sulfonate with amorphous calcium carbonate dispersed therein.These overbased oil-soluble calcium sulfonates are typically clear andbright and have Newtonian rheology. In some cases, they may be slightlyturbid, but such variations do not prevent their use in preparingoverbased calcium sulfonate greases. For the purposes of thisdisclosure, the terms “overbased oil-soluble calcium sulfonate” and“oil-soluble overbased calcium sulfonate” and “overbased calciumsulfonate” refer to any overbased calcium sulfonate suitable for makingcalcium sulfonate greases.

Typically the second step (“conversion”) is to add a converting agent oragents to the product of the promotion step, along with a suitable baseoil (such as mineral oil) if needed to keep the initial grease frombeing too hard, to convert the amorphous calcium carbonate contained inthe overbased calcium sulfonate to a very finely divided dispersion ofcrystalline calcium carbonate (calcite). Prior art converting agentsinclude water and non-aqueous converting agents, such as propyleneglycol, iso-propyl alcohol, formic acid or acetic acid. When acetic acidor other acids are used as a converting agent, typically water andanother non-aqueous converting agent (a third converting agent, such asan alcohol) are also used; alternatively only water (without the thirdconverting agent) is added, but the conversion then typically occurs ina pressurized vessel. Because an excess of calcium hydroxide or calciumoxide is used to achieve overbasing, a small amount of residual calciumoxide or calcium hydroxide may also be present as part of the oilsoluble overbased calcium sulfonate and will be dispersed in the initialgrease structure. The extremely finely divided calcium carbonate formedby conversion, also known as a colloidal dispersion, interacts with thecalcium sulfonate to form a grease-like consistency. Such overbasedcalcium sulfonate greases produced through the two-step process havecome to be known as “simple calcium sulfonate greases” and aredisclosed, for example, in U.S. Pat. Nos. 3,242,079; 3,372,115;3,376,222, 3,377,283; and 3,492,231.

It is also known in the prior art to combine these two steps, bycarefully controlling the reaction, into a single step. In this one-stepprocess, the simple calcium sulfonate grease is prepared by reaction ofan appropriate sulfonic acid with either calcium hydroxide or calciumoxide in the presence of carbon dioxide and a system of reagents thatsimultaneously act as both promoter (creating the amorphous calciumcarbonate overbasing by reaction of carbon dioxide with an excess amountof calcium oxide or calcium hydroxide) and converting agents (convertingthe amorphous calcium carbonate to very finely divided crystallinecalcium carbonate). Thus, the grease-like consistency is formed in asingle step wherein the overbased, oil-soluble calcium sulfonate (theproduct of the first step in the two-step process) is never actuallyformed and isolated as a separate product. This one-step process isdisclosed, for example, in U.S. Pat. Nos. 3,661,622; 3,671,012;3,746,643; and 3,816,310.

In addition to simple calcium sulfonate greases, calcium sulfonatecomplex greases are also known in the prior art. These complex greasesare typically produced by adding a strong calcium-containing base, suchas calcium hydroxide or calcium oxide, to the simple calcium sulfonategrease produced by either the two-step or one-step process and reactingwith up to stoichiometrically equivalent amounts of complexing acids,such as 12-hydroxystearic acid, boric acid, acetic acid (which may alsobe a converting agent when added pre-conversion), or phosphoric acid.The claimed advantages of the calcium sulfonate complex grease over thesimple grease include reduced tackiness, improved pumpability, andimproved high temperature utility. Calcium sulfonate complex greases aredisclosed, for example, in U.S. Pat. Nos. 4,560,489; 5,126,062;5,308,514; and 5,338,467.

Additionally, it is desirable to have a calcium sulfonate complex greasecomposition and method of manufacture that results in both improvedthickener yield (by requiring a smaller percentage of overbased calciumsulfonate in the final grease) and dropping point. The term “thickeneryield” as used herein refers to the concentration of the highlyoverbased oil-soluble calcium sulfonate required to provide a greasewith a specific desired consistency as measured by the standardpenetration tests ASTM D217 or D1403 commonly used in lubricating greasemanufacturing. The term “dropping point” as used herein refers to thevalue obtained by using the standard dropping point test ASTM D2265commonly used in lubricating grease manufacturing. Many of the knownprior art compositions and methodologies require an amount of overbasedcalcium sulfonate of least 36% (by weight of the final grease product)to achieve a suitable grease in the NLGI No. 2 category with ademonstrated dropping point of at least 575 F. The overbased oil-solublecalcium sulfonate is one of the most expensive ingredients in makingcalcium sulfonate grease. Therefore it is desirable to reduce the amountof this ingredient while still maintaining a desirable level of firmnessin the final grease (thereby improving thickener yield).

There are several known compositions and methods that result in improvedthickener yield while maintaining a sufficiently high dropping point.For example, in order to achieve a substantial reduction in the amountof overbased calcium sulfonate used, many prior art references utilize apressure reactor. It is desirable to have an overbased calcium sulfonategrease wherein the percentage of overbased oil-soluble calcium sulfonateis less than 36% and the dropping point is consistently 575 F or higherwhen the consistency is within an NLGI No. 2 grade (or the worked 60stroke penetration of the grease is between 265 and 295), withoutrequiring a pressure reactor. Higher dropping points are considereddesirable since the dropping point is the first and most easilydetermined guide as to the high temperature utility limitations of alubricating grease.

Overbased calcium sulfonate greases requiring less than 36% overbasedcalcium sulfonate are also achieved using the compositions and methodsdescribed in U.S. Pat. Nos. 9,273,265 and 9,458,406. The '265 and '406patents teach the use of added crystalline calcium carbonate and/oradded calcium hydroxyapatite (either with or without added calciumhydroxide or calcium oxide) as calcium-containing bases for reactionwith complexing acids in making complex overbased calcium sulfonategreases. Prior to these patents, the known prior art always taught theuse of calcium oxide or calcium hydroxide as the sources of basiccalcium for production of calcium sulfonate greases or as a requiredcomponent for reacting with complexing acids to form calcium sulfonatecomplex greases. The known prior art also taught that the addition ofcalcium hydroxide or calcium oxide needs to be in an amount sufficient(when added to the amount of calcium hydroxide or calcium oxide presentin the overbased oil-soluble calcium sulfonate) to provide a total levelof calcium hydroxide or calcium oxide sufficient to fully react with thecomplexing acids. The known prior art also generally taught that thepresence of calcium carbonate (as a separate ingredient or as an“impurity” in the calcium hydroxide or calcium oxide, other than thatpresence of the amorphous calcium carbonate dispersed in the calciumsulfonate after carbonation), should be avoided for at least tworeasons. The first being that calcium carbonate is generally consideredto be a weak base, unsuitable for reacting with complexing acids to formoptimum grease structures. The second being that the presence ofunreacted solid calcium compounds (including calcium carbonate, calciumhydroxide or calcium oxide) interferes with the conversion process,resulting in inferior greases if the unreacted solids are not removedprior to conversion or before conversion is completed. However, asdescribed in the '265 and '406 patents, Applicant has found that theaddition of calcium carbonate as a separate ingredient (in addition tothe amount of calcium carbonate contained in the overbased calciumsulfonate), calcium hydroxyapatite, or a combination thereof, eitherwith or without added calcium hydroxide or calcium oxide, as ingredientsfor reacting with complexing acids produces a superior grease

In addition to the '265 and '406 patents, there are a couple of priorart references that disclose the addition of crystalline calciumcarbonate as a separate ingredient (in addition to the amount of calciumcarbonate contained in the overbased calcium sulfonate), but thosegreases have poor thickener yield (as the prior art teaches) or requirenano-sized particles of calcium carbonate. For example, U.S. Pat. No.5,126,062 discloses the addition of 5-15% calcium carbonate as aseparate ingredient in forming a complex grease, but also requires theaddition of calcium hydroxide to react with complexing acids. The addedcalcium carbonate is not the sole added calcium containing base forreacting with complexing acids in the '062 patent. In fact, the addedcalcium carbonate is specifically not added as a basic reactant forreaction with complexing acids. Instead, added calcium hydroxide isrequired as the specific calcium-containing base for reaction with allthe complexing acids. Additionally, the resulting NLGI No. 2 greasecontains 36%-47.4% overbased calcium sulfonate, which is a substantialamount of this expensive ingredient. In another example, Chinesepublication CN101993767, discloses the addition of nano-sized particlesof calcium carbonate (sized between 5-300 nm) being added to theoverbased calcium sulfonate, although the reference does not indicatethat the nano-sized particles of calcium carbonate are added as areactant, or the sole separately added calcium containing base, forreacting with complexing acids. The use of nano-sized particles wouldadd to the thickening of the grease to keep it firm, much like the finedispersion of crystalline calcium carbonate formed by converting theamorphous calcium carbonate contained within the overbased calciumsulfonate (which can be around 20 A to 5000 A or around 2 nm to 500 nmaccording to the '467 patent), but would also substantially increase thecosts over larger sized particles of added calcium carbonate. ThisChinese patent application greatly emphasizes the absolute necessity ofthe added calcium carbonate having a true nano particle size. As shownin the example greases according to the invention described in U.S. Pat.No. 9,273,265, superior greases may be formed by the addition of micronsized calcium carbonate without requiring the use of the very expensivenano-sized particles when using added calcium carbonate as one of or thesole added calcium containing base for reacting with complexing acids.

There are also prior art references for using tricalcium phosphate as anadditive in lubricating greases. For instance, U.S. Pat. Nos. 4,787,992;4,830,767; 4,902,435; 4,904,399; and 4,929,371 all teach usingtricalcium phosphate as an additive for lubricating greases. However, itis believed that prior to the '406 patent, no prior art referencestaught the use of calcium hydroxyapatite, having the formula Ca₅(PO₄)₃OHor a mathematically equivalent formula with a melting point of around1100 C, as a calcium-containing base for reaction with acids to makelubricating greases, including calcium sulfonate-based greases. Thereare several prior art references assigned to Showa Shell Sekiyu inJapan, including U.S. Patent Application Publication No. 2009/0305920,that describe greases containing tricalcium phosphate, Ca₃(PO₄)₂, andreference a “hydroxyapatite” having the formula [Ca₃(PO₄)₂]₃.Ca(OH)₂ asa source of tricalcium phosphate. This reference to “hydroxyapatite” isdisclosed as a mixture of tricalcium phosphate and calcium hydroxide,which is not the same as the calcium hydroxyapatite disclosed andclaimed in the '406 patent and herein having the formula Ca₅(PO₄)₃OH ora mathematically equivalent formula with a melting point of around 1100C. Despite the misleading nomenclature, calcium hydroxyapatite,tricalcium phosphate, and calcium hydroxide are each distinct chemicalcompounds with different chemical formulae, structures, and meltingpoints. When mixed together, the two distinct crystalline compoundstricalcium phosphate (Ca₃(PO₄)₂) and calcium hydroxide (Ca(OH)₂) willnot react with each other or otherwise produce the different crystallinecompound calcium hydroxyapatite (Ca₅(PO₄)₃OH). The melting point oftricalcium phosphate (having the formula Ca₃(PO₄)₂) is 1670 C. Calciumhydroxide does not have a melting point, but instead loses a watermolecule to form calcium oxide at 580 C. The calcium oxide thus formedhas a melting point of 2580 C. Calcium hydroxyapatite (having theformula Ca₅(PO₄)₃OH or a mathematically equivalent formula) has amelting point of around 1100 C. Therefore, regardless of how inaccuratethe nomenclature may be, calcium hydroxyapatite is not the same chemicalcompound as tricalcium phosphate, and it is not a simple blend oftricalcium phosphate and calcium hydroxide.

The addition of alkali metal hydroxides in simple calcium soap greases,such as anhydrous calcium-soap thickened greases, is also known. Butprior to the disclosure in U.S. application Ser. No. 15/130,422, it wasnot known to add an alkali metal hydroxide in a calcium sulfonate greaseto provide improved thickener yield and high dropping point, becausethat addition would be considered unnecessary by one of ordinary skillin the art. The reason for adding an alkali metal hydroxide, such assodium hydroxide, in simple calcium soap greases is that the usuallyused calcium hydroxide has poor water solubility and is a weaker basethan the highly water soluble sodium hydroxide. Because of this, thesmall amount of sodium hydroxide dissolved in the added water is said toreact quickly with the soap forming fatty acid (usually12-hydroxystearic acid or a mixture of 12-hydroxystearic acid and anon-hydroxylated fatty acid such as oleic acid) to form the sodium soap.This quick reaction is thought to “get the ball rolling.” However, thedirect reaction of calcium-containing bases such as calcium hydroxidewith fatty acids has never been a problem when making calcium sulfonatecomplex greases. The reaction occurs very easily, likely due to the highdetergency/dispersancy of the large amount of calcium sulfonate present.As such, it is not known in the prior art to use an alkali metalhydroxide in a calcium sulfonate grease as a way to get the complexingacids to react with the calcium hydroxide.

It has not previously been known to make a calcium magnesium sulfonategrease without a conventional non-aqueous converting agent. It is alsonot known to combine various ingredients and methodologies in making asulfonate-based grease with improved thickener yield and high dropping,such as combining omission of a conventional non-aqueous convertingagent with (1) a split addition of magnesium sulfonate method or adelayed addition of magnesium sulfonate method or a combination of asplit addition and delayed addition method; (2) the use of calciumhydroxyapatite, added crystalline calcium carbonate, or a combinationthereof (without or without added calcium hydroxide or calcium oxide) ascalcium containing bases (also referred to as basic calcium compounds)for reaction with complexing acids; (3) addition of an alkali metalhydroxide; (4) a facilitating acid delay; or (5) a combination of thesemethods and ingredients.

SUMMARY OF THE INVENTION

This invention relates to calcium magnesium sulfonate greases andmethods for manufacturing such greases without adding a conventionalnon-aqueous converting agent prior to conversion to provide improvementsin both thickener yield (requiring less overbased calcium sulfonatewhile maintaining acceptable penetration measurements) and expected hightemperature utility as demonstrated by dropping point. As used herein, acalcium sulfonate grease (or overbased calcium sulfonate grease)containing overbased magnesium sulfonate is sometimes referred to as acalcium magnesium sulfonate grease, an overbased calcium magnesiumsulfonate grease, or a sulfonate-based grease. As used herein,“conventional non-aqueous converting agents” refers to converting agents(other than water) that solely function as converting agents (ratherthan dual role complexing acids-converting agents) and are added to thecomposition prior to conversion. Such conventional non-aqueousconverting agents may contain some water as a diluent or an impurity.Examples of conventional non-aqueous converting agents include alcohols,ethers, glycols, glycol ethers, glycol polyethers, and other polyhydricalcohols and their derivatives that are added prior to conversion. Suchingredients may be added after conversion, if desired, within the scopeof various embodiments of the invention since they would not be actingas converting agents after conversion is complete and would not beconsidered “conventional non-aqueous converting agents” in that case.

According to one preferred embodiment, a sulfonate-based grease is madeby mixing overbased calcium sulfonate, overbased magnesium sulfonate, anoptional base oil, and water as a converting agent, without thepre-conversion addition of any conventional non-aqueous convertingagents (such a hexylene glycol). The magnesium sulfonate may be addedall at once, using a split addition method, a magnesium sulfonate delayaddition method, or a combination of a split addition and delayedaddition method (as further described in co-pending U.S. applicationSer. No. 15/593,792, which is incorporated herein by reference). Withoutbeing bound by theory, it appears that the magnesium sulfonate acts as aconverting agent. Since magnesium sulfonate has not previously beenknown to be used as a converting agent, it is sometimes referred toherein as a “non-conventional” converting agent.

According to another preferred embodiment, if a complex grease isdesired, one or more complexing acids are also added, either beforeconversion, after conversion, or both. Some complexing acids are knownto also act as converting agents when added prior to conversion. Dualrole converting agent-complexing acids are not considered to beconventional non-aqueous converting agents herein and may be added priorto conversion according to various embodiments of the invention,provided that magnesium sulfonate is also added and no conventionalnon-aqueous converting agents are added.

According to another preferred embodiment, improved thickener yield andsufficiently high dropping points are achieved when conventionalnon-aqueous converting agents are omitted, even when the overbasedcalcium sulfonate is considered to be of “poor” quality as described anddefined in the '406 patent. According to other preferred embodiments, asulfonate-based grease is made without adding any conventionalnon-aqueous converting agents prior to conversion in combination withone or more of the following ingredients or methods: (1) the addition ofcalcium hydroxyapatite and/or added calcium carbonate ascalcium-containing bases for reacting with complexing acids, either withor without separately adding added calcium hydroxide and/or addedcalcium oxide as calcium containing bases; (2) the addition of an alkalimetal hydroxide (most preferably lithium hydroxide); or (3) afacilitating acid delay. These additional methods and ingredients aredisclosed in U.S. patent application Ser. No. 13/664,768 (now U.S. Pat.No. 9,458,406), Ser. No. 13/664,574 (now U.S. Pat. No. 9,273,265), Ser.Nos. 15/130,422, 15/593,792, and 15/593,839, which are incorporatedherein by reference. For ease of reference, a delay with respect to theaddition of overbased magnesium sulfonate as described in the '792application will be referred to as a magnesium sulfonate delay period ormagnesium sulfonate delay method (or similar wording); and a delay withrespect to a facilitating acid as described in the '839 application willbe referred to as a facilitating acid delay period or facilitating aciddelay method (or similar wording).

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Sulfonate-Based Grease Compositions

According to one preferred embodiment of the invention, a calciummagnesium sulfonate grease composition is provided comprising overbasedcalcium sulfonate, overbased magnesium sulfonate, water as a convertingagent, and no conventional non-aqueous converting agents are added asingredients to the composition. In other words, water, magnesiumsulfonate, and optionally any dual role complexing acid-convertingagents are the only converting agent ingredients added to thecomposition. According to another preferred embodiment, a calciummagnesium sulfonate simple or complex grease composition furthercomprises base oil, one or more added calcium containing bases, andoptionally a facilitating acid. According to another preferredembodiment, a calcium magnesium sulfonate complex grease compositionfurther comprises one or more complexing acids.

According to several preferred embodiments, a calcium sulfonate greasecomposition or a calcium magnesium sulfonate grease compositioncomprises the following ingredients by weight percent of the finalgrease product (although some ingredients, such as water, acids, andcalcium containing bases, may not be in the final grease product or maynot be in the concentrations indicated for addition):

TABLE 1 Preferred Compositions Preferred More Preferred Most PreferredIngredient Amount (%) Amount (%) Amount (%) Overbased   10%-45%  10%-36%   10%-22% Calcium Sulfonate Overbased  0.1%-30   1%-24%  1%-15% Magnesium Sulfonate Added Base Oil   30%-70%   45%-70%  50%-70% Total Added  2.7%-41.2% 4.15% to 31% 6.18% to 20.8% CalciumContaining Bases (Optional for a Simple Grease) Water (as a  1.5%-10% 2.0%-5.0%  2.2%-4.5% Converting Agent) Facilitating Acid  0.5%-5.0% 1.0%-4.0%  1.3%-3.6% Alkali Metal 0.005% to 0.5% 0.01% to 0.4% 0.02% to0.2% Hydroxide (Optional) Total Complexing 1.25%-18% 2.2-12% 3.55%-8.5%Acids (if complex grease is desired)

Some or all of any particular ingredient, including converting agentsand added calcium containing bases, may not be in the final finishedproduct due to evaporation, volatilization, or reaction with otheringredients during manufacture. These amounts are when a grease is madein an open vessel. Even smaller amounts of overbased calcium sulfonatemay be used when a calcium magnesium sulfonate grease is made in apressure vessel.

According to another preferred embodiment, a calcium magnesium sulfonategrease comprises overbased calcium sulfonate and overbased magnesiumsulfonate as ingredients in a ratio range of 100:0.1 to 60:40, morepreferably in a ratio range of 99:1 to 70/30, and most preferably in aratio range of 90:10 to 80:20. According to another preferredembodiment, a pre-conversion sulfonate-based grease compositioncomprises the following ingredients: overbased calcium sulfonate,overbased magnesium sulfonate, water, and optional base oil, and whereinwater is the sole conventional converting agent in the pre-conversioncomposition. According to another preferred embodiment, a apre-conversion sulfonate-based grease composition comprises overbasedcalcium sulfonate and overbased magnesium sulfonate as ingredients in aratio range of 100:0.1 to 60:40, more preferably in a ratio range of99:1 to 70/30, and most preferably in a ratio range of 90:10 to 80:20.

The highly overbased oil-soluble calcium sulfonate (also referred toherein as simply “calcium sulfonate” or “overbased calcium sulfonate”for brevity) used according to these embodiments of the invention can beany typical to that documented in the prior art, such as U.S. Pat. Nos.4,560,489; 5,126,062; 5,308,514; and 5,338,467. The highly overbasedoil-soluble calcium sulfonate may be produced in situ according to suchknown methods or may be purchased as a commercially available product.Such highly overbased oil-soluble calcium sulfonates will have a TotalBase Number (TBN) value not lower than 200, preferably not lower than300, and most preferably about 400 or higher. Commercially availableoverbased calcium sulfonates of this type include, but are not limitedto, the following: Hybase C401 as supplied by Chemtura USA Corporation;Syncal OB 400 and Syncal OB405-WO as supplied by Kimes TechnologiesInternational Corporation; Lubrizol 75GR, Lubrizol 75NS, Lubrizol 75P,and Lubrizol 75WO as supplied by Lubrizol Corporation. The overbasedcalcium sulfonate contains around 28% to 40% dispersed amorphous calciumcarbonate by weight of the overbased calcium sulfonate, which isconverted to crystalline calcium carbonate during the process of makingthe calcium sulfonate grease. The overbased calcium sulfonate alsocontains around 0% to 8% residual calcium oxide or calcium hydroxide byweight of the overbased calcium sulfonate. Most commercial overbasedcalcium sulfonates will also contain around 40% base oil as a diluent,to keep the overbased calcium sulfonate from being so thick that it isdifficult to handle and process. The amount of base oil in the overbasedcalcium sulfonate may make it unnecessary to add additional base oil (asa separate ingredient) prior to conversion to achieve an acceptablegrease.

The overbased calcium sulfonate used may be of a “good” quality or a“poor” quality as defined in the '406 patent and herein. Certainoverbased oil-soluble calcium sulfonates marketed and sold for themanufacture of calcium sulfonate-based greases can provide products withunacceptably low dropping points when prior art calcium sulfonatetechnologies are used. Such overbased oil-soluble calcium sulfonates arereferred to as “poor quality” overbased oil-soluble calcium sulfonatesthroughout this application. When all ingredients and methods are thesame except for the commercially available batch of overbased calciumsulfonate used, overbased oil-soluble calcium sulfonates producinggreases having higher dropping points (above 575 F) are considered to be“good” quality calcium sulfonates for purposes of this invention, andthose producing greases having lower dropping points are considered tobe “poor” quality for purposes of this invention. Several examples ofthis are provided in the '406 patent, which is incorporated byreference. Although comparative chemical analyses of good quality andpoor quality overbased oil-soluble calcium sulfonates has beenperformed, it is believed that the precise reason for this low droppingpoint problem has not been proven. While many commercially availableoverbased calcium sulfonates are considered to be good quality, it isdesirable to achieve both improved thickener yield and higher droppingpoints regardless of whether a good quality or a poor quality calciumsulfonate is used. It has been found that both improved thickener yieldand higher dropping point may be achieved with either a good quality ora poor quality calcium sulfonate when an alkali metal hydroxide is used,particularly in combination with the delayed converting agent addition,split magnesium sulfonate addition, and delayed magnesium sulfonateaddition methods according to the invention.

Any petroleum-based naphthenic or paraffinic mineral oils commonly usedand well known in the grease making art may be used as the base oilaccording to the invention. Base oil is added as needed, since mostcommercial overbased calcium sulfonates will already contain about 40%base oil as a diluent so as to prevent the overbased sulfonate frombeing so thick that it cannot be easily handled. Similarly, overbasedmagnesium sulfonate will likely contain base oil as a diluent. With theamount of base oil in the overbased calcium sulfonate and overbasedmagnesium sulfonate, it may be unnecessary to add additional base oildepending on the desired consistency of the grease immediately afterconversion as well as the desired consistency of the final grease.Synthetic base oils may also be used in the greases of the presentinvention. Such synthetic base oils include polyalphaolefins (PAO),diesters, polyol esters, polyethers, alkylated benzenes, alkylatednaphthalenes, and silicone fluids. In some cases, synthetic base oilsmay have an adverse effect if present during the conversion process aswill be understood by those of ordinary skill in the art. In such cases,those synthetic base oils should not be initially added, but added tothe grease making process at a stage when the adverse effects will beeliminated or minimized, such as after conversion. Naphthenic andparaffinic mineral base oils are preferred due to their lower cost andavailability. The total amount of base oil added (including thatinitially added and any that may be added later in the grease process toachieve the desired consistency) is preferably in the ranges indicatedin Table 1 above, based on the final weight of the grease. Typically,the amount of base oil added as a separate ingredient will increase asthe amount of overbased calcium sulfonate decreases. Combinations ofdifferent base oils as described above may also be used in theinvention, as will be understood by those with ordinary skill in theart.

The overbased magnesium sulfonate (also referred to herein as simply“magnesium sulfonate,” for brevity) used according to these embodimentsof the invention for a calcium magnesium sulfonate grease can be anytypical to that documented or known in the prior art. The overbasedmagnesium sulfonate may be made in-situ or any commercially availableoverbased magnesium sulfonate may be used. Overbased magnesium sulfonatewill typically comprise a neutral magnesium alkylbenzene sulfonate andan amount of overbasing wherein a substantial amount of that overbasingis in the form of magnesium carbonate. The magnesium carbonate isbelieved to typically be in an amorphous (non-crystalline) form. Theremay also be a portion of the overbasing that is in the form of magnesiumoxide, magnesium hydroxide, or a mixture of the oxide and hydroxide. Thetotal base number (TBN) of the overbased magnesium sulfonates ispreferably at least 400 mg KOH/gram, but lower TBN values may also beacceptable and in the same ranges as indicated for the TBN values forthe overbased calcium sulfonate above.

Although not required, a small amount of a facilitating acid mayoptionally be added to the mixture prior to conversion according toanother embodiment of the invention. Suitable facilitating acids, suchas an alkyl benzene sulfonic acid, having an alkyl chain lengthtypically between 8 to 16 carbons, may help to facilitate efficientgrease structure formation. Most preferably, this alkyl benzene sulfonicacid comprises a mixture of alkyl chain lengths that are mostly about 12carbons in length. Such benzene sulfonic acids are typically referred toas dodecylbenzene sulfonic acid (“DDBSA”). Commercially availablebenzene sulfonic acids of this type include JemPak 1298 Sulfonic Acid assupplied by JemPak GK Inc., Calsoft LAS-99 as supplied by Pilot ChemicalCompany, and Biosoft S-101 as supplied by Stepan Chemical Company. Whenthe alkyl benzene sulfonic acid is used in the present invention, it isadded before conversion and preferably in an amount in the rangesindicated in Table 1. If the calcium sulfonate is made in situ usingalkyl benzene sulfonic acid, the facilitating acid added according tothis embodiment is in addition to that required to produce the calciumsulfonate

Water is added to the preferred embodiments of the invention as oneconverting agent. The total amount of water added as a converting agent,based on the final weight of the grease, is preferably in the rangesindicated in Table 1. Additional water may be added after conversion.Also, if the conversion takes place in an open vessel at a sufficientlyhigh temperature so as to volatilize a significant portion of the waterduring conversion, additional water may be added to replace the waterthat was lost. Conventional non-aqueous converting agents, which aretypically added to calcium sulfonate greases, are not used asingredients according to preferred embodiments of the invention. Suchconventional non-aqueous converting agents include alcohols, ethers,glycols, glycol ethers, glycol polyethers, and other polyhydric alcoholsand their derivatives. These ingredients may be added after conversionis complete, if desired, within the scope of the invention since theywill not act as converting agents if added after conversion; however, itis preferred that they be omitted altogether.

One or more calcium containing bases are also added as ingredients in apreferred embodiment of a calcium magnesium sulfonate grease compositionaccording to the invention. These calcium containing bases react withcomplexing acids to form a complex calcium magnesium sulfonate grease.The calcium containing bases may include calcium hydroxyapatite, addedcalcium carbonate, added calcium hydroxide, added calcium oxide, or acombination of one or more of the foregoing. Most preferably addedcalcium hydroxyapatite and added calcium carbonate are used together,along with a small amount of added calcium hydroxide. The preferredamounts of these three added calcium containing bases as ingredients byweight percent of the final grease product (although these bases willreact with acids and will not be present in the final grease product)according to this preferred embodiment are:

TABLE 2 Preferred Added Calcium Containing Bases Preferred MorePreferred Most Preferred Ingredient Amount (%) Amount (%) Amount (%)Calcium  1.0-20 2.0-15  3.0-10  Hydroxyapatite Added Calcium  1.0-202.0-15  3.0-10  Carbonate Added Calcium 0.07-1.2 0.15-1.00 0.18-0.80Hydroxide or Calcium Oxide

The calcium hydroxyapatite used as a calcium containing base forreacting with complexing acids according to preferred embodiments may beadded pre-conversion, post-conversion, or a portion added pre- and aportion added post-conversion. Most preferably, the calciumhydroxyapatite is finely divided with a mean particle size of around 1to 20 microns, preferably around 1 to 10 microns, most preferably around1 to 5 microns. Furthermore, the calcium hydroxyapatite will be ofsufficient purity so as to have abrasive contaminants such as silica andalumina at a level low enough to not significantly impact the anti-wearproperties of the resulting grease. Ideally, for best results, thecalcium hydroxyapatite should be either food grade or U.S. Pharmacopeiagrade. The amount of calcium hydroxyapatite added will preferably be inthe ranges indicated in Tables 1 (total calcium containing bases) or 2,although more can be added, if desired, after conversion and allreaction with complexing acids is complete.

According to another preferred embodiment of the invention, calciumhydroxyapatite may be added in an amount that is stoichiometricallyinsufficient to fully react with the complexing acids. In thisembodiment, finely divided calcium carbonate as an oil-insoluble, solid,added calcium-containing base may be added, preferably beforeconversion, in an amount sufficient to fully react with and neutralizethe portion of any subsequently added complexing acids not neutralizedby the calcium hydroxyapatite.

According to another preferred embodiment, calcium hydroxyapatite may beadded in an amount that is stoichiometrically insufficient to fullyreact with the complexing acids. In this embodiment, finely dividedcalcium hydroxide and/or calcium oxide as an oil-insoluble solidcalcium-containing base may be added, preferably before conversion, inan amount sufficient to fully react with and neutralize the portion ofany subsequently added complexing acids not neutralized by the co-addedcalcium hydroxyapatite. According to yet another preferred embodiment,when calcium hydroxyapatite is used in combination with added calciumhydroxide as calcium containing bases for reacting with complexing acidsto make a calcium magnesium sulfonate grease, a smaller amount ofcalcium hydroxyapatite is needed compared to the greases described inthe '406 patent. In the '406 patent, the added calcium hydroxide and/orcalcium oxide are preferably present in an amount not more than 75% ofthe hydroxide equivalent basicity provided by the total of the addedcalcium hydroxide and/or calcium oxide and the calcium hydroxyapatite.In other words, the calcium hydroxyapatite contributes preferably atleast 25% of the total added hydroxide equivalents (from both calciumhydroxyapatite and added calcium hydroxide and/or added calcium oxide)in the greases described in the '406 patent, particularly when a poorquality overbased calcium sulfonate is used. If less than that amount ofcalcium hydroxyapatite is used, the dropping point of the final greasemay suffer. However, with the addition of overbased magnesium sulfonateto the composition according to various embodiments of this invention,less calcium hydroxyapatite may be used while still maintainingsufficiently high dropping points. The amount of calcium hydroxyapatiteused according to preferred embodiments of this invention may be lessthan 25%, and even less than 10% of the hydroxide equivalent basicity,even when a poor quality overbased calcium sulfonate is used. This isone indication that the presence of overbased magnesium sulfonate in thefinished grease has resulted in an unexpected changed and improvedchemical structure not anticipated by the prior art. Since calciumhydroxyapatite is typically much more costly compared to added calciumhydroxide, this results in a further potential cost reduction for thefinal grease without any significant reduction in dropping point.

In another embodiment, calcium carbonate may also be added with thecalcium hydroxyapatite, calcium hydroxide and/or calcium oxide, with thecalcium carbonate being added either before or after reacting withcomplexing acids, or added both before and after reacting withcomplexing acids. When the amounts of calcium hydroxyapatite, calciumhydroxide, and/or calcium oxide are not sufficient to neutralize thecomplexing acid or acids added, calcium carbonate is preferably added inan amount that is more than sufficient to neutralize any remainingcomplexing acid or acids.

The added calcium carbonate used as a calcium containing base, eitheralone or in combination with another calcium containing base or bases,according to these embodiments of the invention, is finely divided witha mean particle size of around 1 to 20 microns, preferably around 1 to10 microns, most preferably around 1 to 5 microns. Furthermore, theadded calcium carbonate is preferably crystalline calcium carbonate(most preferably calcite) of sufficient purity so as to have abrasivecontaminants such as silica and alumina at a level low enough to notsignificantly impact the anti-wear properties of the resulting grease.Ideally, for best results, the calcium carbonate should be either foodgrade or U.S. Pharmacopeia grade. The amount of added calcium carbonateadded is preferably in the ranges indicated in Tables 1 (total calciumcontaining bases) or 2. These amounts are added as a separate ingredientin addition to the amount of dispersed calcium carbonate contained inthe overbased calcium sulfonate. According to another preferredembodiment of the invention, the added calcium carbonate is added priorto conversion as the sole added calcium-containing base ingredient forreacting with complexing acids. Additional calcium carbonate may beadded to either the simple or complex grease embodiments of theinvention after conversion, and after all reaction with complexing acidsis complete in the case of a complex grease. However, references toadded calcium carbonate herein refer to the calcium carbonate that isadded prior to conversion and as one of or the sole addedcalcium-containing base for reaction with complexing acids when making acomplex grease according to the invention.

The added calcium hydroxide and/or added calcium oxide addedpre-conversion or post-conversion according to another embodiment shallbe finely divided with a mean particle size of around 1 to 20 microns,preferably around 1 to 10 microns, most preferably around 1 to 5microns. Furthermore, the calcium hydroxide and calcium oxide will be ofsufficient purity so as to have abrasive contaminants such as silica andalumina at a level low enough to not significantly impact the anti-wearproperties of the resulting grease. Ideally, for best results, thecalcium hydroxide and calcium oxide should be either food grade or U.S.Pharmacopeia grade. The total amount of calcium hydroxide and/or calciumoxide will preferably be in the ranges indicated in Tables 1 (totalcalcium containing bases) or 2. These amounts are added as separateingredients in addition to the amount of residual calcium hydroxide orcalcium oxide contained in the overbased calcium sulfonate. Mostpreferably, an excess amount of calcium hydroxide relative to the totalamount of complexing acids used is not added prior to conversion.According to yet another embodiment, it is not necessary to add anycalcium hydroxide or calcium oxide for reacting with complexing acidsand either added calcium carbonate or calcium hydroxyapatite (or both)may be used as the sole added calcium containing base(s) for suchreaction or may be used in combination for such reaction.

One or more alkali metal hydroxides are also optionally added asingredients in a preferred embodiment of a calcium magnesium sulfonategrease composition according to the invention. The optional added alkalimetal hydroxides comprise sodium hydroxide, lithium hydroxide, potassiumhydroxide, or a combination thereof. Most preferably, lithium hydroxideis the alkali hydroxide used with the overbased calcium magnesiumsulfonate greases according to one embodiment of the invention. Incombination with the added overbased magnesium sulfonate, lithiumhydroxide may work as well as, or better than, sodium hydroxide. This isunexpected since lithium hydroxide appeared not to work as well assodium hydroxide when only overbased calcium sulfonate is used, asdisclosed in the '422 application. This is yet another indication thatthe presence of overbased magnesium sulfonate in the final grease hasresulted in an unexpected property not anticipated by the prior art. Thetotal amount of alkali metal hydroxide added is preferably in the rangesindicated in Table 1. As with the calcium-containing bases, the alkalimetal hydroxide reacts with complexing acids resulting in an alkalimetal salt of a complexing acid present in the final grease product. Thepreferred amounts indicated above are amounts added as raw ingredientsrelative to the weight of the final grease product, even though noalkali metal hydroxide will be present in the final grease.

According to one preferred embodiment of a method for making anoverbased calcium magnesium sulfonate grease, the alkali metal hydroxideis dissolved in the water prior to being added to other ingredients. Thewater used to dissolve the alkali metal hydroxide may be water used as aconverting agent or water added post-conversion. It is most preferred todissolve the alkali metal hydroxide in water prior to adding it to theother ingredients, but it may also be directly added to the otheringredients without first dissolving it in water.

One or more complexing acids, such as long chain carboxylic acids, shortchain carboxylic acids, boric acid, and phosphoric acid are also addedwhen a complex calcium magnesium sulfonate grease is desired. Apreferred range of total complexing acids is around 1.25% to 18% andpreferred amounts for specific types of complexing acids as ingredientsby weight percent of the final grease product (although these acids willreact with bases and will not be present in the final grease product)are:

TABLE 3 Preferred Complexing Acids Preferred More Preferred MostPreferred Ingredient Amount (%) Amount (%) Amount (%) Short Chain Acids0.05-2.0 0.1-1.0 0.15-0.5 Long Chain Acids  0.5-8.0 1.0-5.0  2.0-4.0Boric Acid  0.3-4.0 0.5-3.0  0.6-2.0 Phosphoric Acid  0.4-4.0 0.6-3.0 0.8-2.0

The long chain carboxylic acids suitable for use in accordance with theinvention comprise aliphatic carboxylic acids with at least 12 carbonatoms. Preferably, the long chain carboxylic acids comprise aliphaticcarboxylic acids with at least 16 carbon atoms. Most preferably, thelong chain carboxylic acid is 12-hydroxystearic acid. The total amountof long chain carboxylic acid(s) is preferably in the ranges indicatedin Table 3.

Short chain carboxylic acids suitable for use in accordance with theinvention comprise aliphatic carboxylic acids with no more than 8 carbonatoms, and preferably no more than 4 atoms. Most preferably, the shortchain carboxylic acid is acetic acid. The total amount of short chaincarboxylic acids is preferably in the ranged indicated in Table 3. Anycompound that can be expected to react with water or other componentsused in producing a grease in accordance with this invention with suchreaction generating a long chain or short chain carboxylic acid are alsosuitable for use. For instance, using acetic anhydride would, byreaction with water present in the mixture, form the acetic acid to beused as a complexing acid. Likewise, using methyl 12-hydroxystearatewould, by reaction with water present in the mixture, form the12-hydroxystearic acid to be used as a complexing acid. Alternatively,additional water may be added to the mixture for reaction with suchcomponents to form the necessary complexing acid if sufficient water isnot already present in the mixture. Additionally, acetic acid and othercarboxylic acids may be used as a converting agent or complexing acid orboth, depending on when it is added. Similarly, some complexing acids(such as the 12-hydroxystearic acid in the '514 and '467 patents) mayalso be used as converting agents.

If boric acid is used as a complexing acid according to this embodiment,the amount is preferably in the ranges indicated in Table 3. The boricacid may be added after first being dissolved or slurried in water, orit can be added without water. Preferably, the boric acid will be addedduring the manufacturing process such that water is still present.Alternatively, any of the well-known inorganic boric acid salts may beused instead of boric acid. Likewise, any of the established boratedorganic compounds such as borated amines, borated amides, boratedesters, borated alcohols, borated glycols, borated ethers, boratedepoxides, borated ureas, borated carboxylic acids, borated sulfonicacids, borated epoxides, borated peroxides and the like may be usedinstead of boric acid. If phosphoric acid is used as a complexing acid,an amount preferably in the ranges indicated in Table 3 is added. Thepercentages of various complexing acids described herein refer to pure,active compounds. If any of these complexing acids are available in adiluted form, they may still be suitable for use in the presentinvention. However, the percentages of such diluted complexing acidswill need to be adjusted so as to take into account the dilution factorand bring the actual active material into the specified percentageranges.

Other additives commonly recognized within the grease making art mayalso be added to either the simple grease embodiment or the complexgrease embodiment of the invention. Such additives can include rust andcorrosion inhibitors, metal deactivators, metal passivators,antioxidants, extreme pressure additives, antiwear additives, chelatingagents, polymers, tackifiers, dyes, chemical markers, fragranceimparters, and evaporative solvents. The latter category can beparticularly useful when making open gear lubricants and braided wirerope lubricants. The inclusion of any such additives is to be understoodas still within the scope of the present invention. All percentages ofingredients are based on the final weight of the finished grease unlessotherwise indicated, even though that amount of the ingredient may notbe in the final grease product due to reaction or volatilization.

The calcium sulfonate complex greases according to these preferredembodiments are an NLGI No. 2 grade grease having a dropping point of atleast 575 F more preferably of 650 F or greater, but greases with otherNLGI grades from No. 000 to No. 3 may also be made according to theseembodiments with modifications as will be understood by those ofordinary skill in the art. The use of the preferred methods andingredients according to the invention appear to improve hightemperature shear stability compared to most calcium sulfonate-basedgreases (that are 100% based on calcium).

Methods of Making Sulfonate-Based Greases without a Pre-ConversionAddition of a Conventional Non-Aqueous Converting Agent

The calcium magnesium sulfonate grease compositions are preferably madeaccording to the methods of the invention described herein. In onepreferred embodiment, the method comprises: (1) mixing overbased calciumsulfonate and a base oil; (2) adding and mixing overbased magnesiumsulfonate, which may be added all at once prior to conversion, addedusing a split addition method, added using a magnesium sulfonate delayperiod, or added using a combination of split addition and magnesiumsulfonate delay period(s); (3) optionally adding and mixing an alkalimetal hydroxide, preferably pre-dissolved in water prior to adding tothe other ingredients; (4) adding and mixing one or more calciumcontaining bases; (5) adding and mixing water as a converting agent,which may include the water from step 3 if added prior to conversion,and omitting any pre-conversion addition of conventional non-aqueousconverting agents; (6) optionally adding and mixing one or morefacilitating acids; (7) adding and mixing one or more complexing acids,if a complex calcium magnesium grease is desired; and (8) heating somecombination of these ingredients until conversion has occurred.Additional optional steps comprises: (9) optionally mixing additionalbase oil, as needed, after conversion; (10) mixing and heating to atemperature sufficiently high to insure removal of water and anyvolatile reaction byproducts and optimize final product quality; (11)cooling the grease while adding additional base oil as needed; (12)adding remaining desired additives as are well known in the art; and, ifdesired, (13) milling the final grease as required to obtain a finalsmooth homogenous product.

The added magnesium sulfonate may be added all at once prior toconversion, preferably just after mixing the overbased calcium sulfonateand any added base oil. According to another preferred embodiment, theremay be a magnesium sulfonate delay period, as further described in the'792 application and below, between the addition of water or otherreactive ingredients and at least a portion of the magnesium sulfonateadded prior to conversion. According to another preferred embodiment, aportion of the magnesium sulfonate may be added prior to conversion(preferably at the beginning, just after mixing the overbased calciumsulfonate and any added base oil, or prior to conversion beginning) andanother portion added after conversion (either right after conversion iscomplete or after post-conversion heating and/or cooling of themixture).

Each of the ingredients in steps (3), (4) and (7) can be added prior toconversion, after conversion, or a portion added prior and anotherportion added after conversion. Any facilitating acid added in step (6)is preferably added prior to conversion. If a facilitating acid andalkali metal hydroxide are used, the facilitating acid is preferableadded to the mixture before the alkali metal hydroxide is added. Mostpreferably, the specific ingredients and amounts used in the methods ofthe invention are according to the preferred embodiments of thecompositions described herein. Although some ingredients are preferablyadded prior to other ingredients, the order of addition of ingredientsrelative to other ingredients in the preferred embodiments of theinvention is not critical.

Although the order and timing of these final steps 9-13 is not critical,it is preferred that water be removed quickly after conversion.Generally, the grease is heated (preferably under open conditions, notunder pressure, although pressure may be used) to between 250 F and 300F, preferably 300 F to 380 F, most preferably 380 F to 400 F, to removethe water that was initially added as a converting agent, as well as anywater formed by chemical reactions during the formation of the grease.Having water in the grease batch for prolonged periods of time duringmanufacture may result in degradation of thickener yield, droppingpoint, or both, and such adverse effects may be avoided by removing thewater quickly. If polymeric additives are added to the grease, theyshould preferably not be added until the grease temperature reaches 300F. Polymeric additives can, if added in sufficient concentration, hinderthe effective volatilization of water. Therefore, polymeric additivesshould preferably be added to the grease only after all water has beenremoved. If during manufacture it can be determined that all water hasbeen removed before the temperature of the grease reaches the preferred300 F value, then any polymer additives may preferably be added at anytime thereafter.

Overbased Magnesium Sulfonate Delayed Addition Methods

In one preferred embodiment, there are one or more delay periods betweenthe addition of water or other reactive ingredients (such as acids,bases, or non-aqueous converting agents) and the subsequent addition ofat least a portion of the overbased magnesium sulfonate. In thismagnesium sulfonate delayed addition method, one or more delays mayprecede the addition of all of the magnesium sulfonate or, if a splitaddition method is also used, one or more delay periods may precede anyportion of the magnesium sulfonate added or may precede each portionadded. One or more of the magnesium sulfonate delay periods may be atemperature adjustment delay period or a holding delay period or both.

For example, a first magnesium sulfonate temperature adjustment delayperiod is the amount of time after a portion water or other reactiveingredient is added and prior to the addition of magnesium sulfonatethat it takes to heat the mixture to a temperature or range oftemperatures (the first magnesium sulfonate temperature). A firstmagnesium sulfonate holding delay period is the amount of time themixture is held at the first magnesium sulfonate temperature beforebeing heated or cooled to another temperature or before adding at leasta portion of the magnesium sulfonate. A second magnesium sulfonatetemperature adjustment delay period is the amount of time after thefirst holding delay period that it takes to heat or cool the mixture toanother temperature or temperature range (the second magnesium sulfonatetemperature). A second magnesium sulfonate holding delay period is theamount of time the mixture is held at the second magnesium sulfonatetemperature before being heated or cooled to another temperature orbefore adding at least another portion of magnesium sulfonate.Additional magnesium sulfonate temperature adjustment delay periods ormagnesium sulfonate holding delay periods (i.e. a third magnesiumsulfonate temperature adjustment delay period) follow the same pattern.Generally, the duration of each magnesium sulfonate temperatureadjustment delay period will be about 30 minutes to 24 hours, or moretypically about 30 minutes to 5 hours. However, the duration of anymagnesium sulfonate temperature adjustment delay period will varydepending on the size of the grease batch, the equipment used to mix andheat the batch, and the temperature differential between the startingtemperature and final temperature, as will be understood by those ofordinary skill in the art.

Generally, a magnesium sulfonate holding delay period will be followedor preceded by a temperature adjustment delay period and vice versa, butthere may be two holding delay periods back to back or two temperatureadjustment periods back to back. For example, the mixture may be held atambient temperature for 30 minutes prior to adding a portion ofmagnesium sulfonate and after adding water or a reactive ingredient (afirst magnesium sulfonate holding delay period) and may continue to beheld at ambient temperature for another hour prior to adding moremagnesium sulfonate (a second magnesium sulfonate holding delay period).Additionally, the mixture may be heated or cooled to a first temperatureprior to adding at least a portion of the magnesium sulfonate and afteradding water or another reactive ingredient (a first magnesium sulfonatetemperature adjustment period) and then the mixture is heated or cooledto a second temperature after which more magnesium sulfonate is added (asecond magnesium sulfonate temperature adjustment period, without anyinterim holding period). Additionally, a portion of magnesium sulfonateneed not be added after every delay period, but may skip delay periodsprior to addition or between additions. For example, prior to adding aportion of the magnesium sulfonate, the mixture may be heated to atemperature (first magnesium sulfonate temperature adjustment delayperiod) and then held at that temperature for a period of time (a firstmagnesium sulfonate holding delay period) before a subsequent additionof magnesium sulfonate.

According to one preferred embodiment, the first magnesium sulfonatetemperature may be ambient temperature or another temperature. Anysubsequent magnesium sulfonate temperature may be higher or lower thanthe previous temperature. If a portion of magnesium sulfonate is addedto a mixture including water or other reactive ingredients immediatelyafter the mixture reaches a temperature or range of temperatures, thenthere is no magnesium sulfonate holding time delay for that particulartemperature and that portion of the magnesium sulfonate; but if anotherportion of magnesium sulfonate is added after holding at thattemperature or range of temperatures for a period of time then there isa magnesium sulfonate holding time delay for that temperature and thatportion of the magnesium sulfonate. A portion of magnesium sulfonate maybe added after any magnesium sulfonate temperature adjustment delayperiod or magnesium sulfonate holding delay period and another portionof magnesium sulfonate may be added after another magnesium sulfonatetemperature adjustment delay period or magnesium sulfonate holding delayperiod. Additionally, the addition of water, one reactive ingredient ora portion thereof may be a starting point for one magnesium sulfonatedelay period and a subsequent addition of water, the same reactiveingredient, a different reactive ingredient, or portion thereof may be astarting point for another magnesium sulfonate delay period.

Overbased Magnesium Sulfonate Split Addition Methods

In another preferred embodiment, the total amount of overbased magnesiumsulfonate is added in two parts (a split addition method). The firstportion being added at or near the beginning of the process (beforeconversion is complete, and preferably before conversion begins), andthe second part being added later after the grease structure has formed(after conversion is complete or after post-conversion heating and/orcooling of the mixture). When a split addition method is used, it ispreferred to add around 0.1-20% magnesium sulfonate (based on the finalweight of the grease) in the first part added prior to conversion, morepreferably around 0.5-15%, and most preferably around 1.0-10% in thefirst part. The remainder of the magnesium sulfonate, preferably toprovide total amounts in the ranges indicated in Table 1, would be addedafter conversion. Preferably around 0.25 to 95% of the total magnesiumsulfonate is added in the first part, more preferably around 1.0-75% ofthe total magnesium sulfonate, and most preferably around 10-50% of thetotal magnesium sulfonate is added in the first part.

A split overbased magnesium sulfonate addition method may also becombined with a delayed magnesium sulfonate addition method. In apreferred combined method, a first portion of the overbased magnesiumsulfonate is not added at the very beginning, but after the additionwater or one or more reactive components, and before conversionbegins—with one or more magnesium sulfonate temperature adjustment delayperiod and/or magnesium sulfonate holding delay periods between theaddition of water or other reactive ingredients and the addition of thefirst portion of the magnesium sulfonate. The second portion is thenadded after conversion is complete either before further addition ofwater or additional reactive ingredient(s) (with no additional magnesiumsulfonate delay periods) or after the addition of additional water orother reactive components (another magnesium sulfonate delay period,which may include one or more magnesium sulfonate temperature adjustmentdelay period and/or magnesium sulfonate holding delay periods).

Any of these magnesium sulfonate addition methods may be combined withany facilitating acid delay method, any calcium containing base additionmethod, any alkali metal hydroxide addition method, or any combinationthereof described below.

Facilitating Acid Delay Methods

According to another preferred embodiment, a sulfonate-based greasecompositions are preferably made with a facilitating acid delay period,as described in the '839 application. The preferred steps are the sameas steps (1)-(13) above, except that the addition of a facilitating acidin step (6) is not optional and there are one or more facilitating aciddelay periods between the addition of the facilitating acid(s) and atleast a portion of another ingredient (the next subsequently addedingredient). The facilitating acid added in step 6 is added prior toconversion. If an alkali metal hydroxide is used, the facilitating acidis preferable added to the mixture before the alkali metal hydroxide isadded.

A facilitating acid delay period may be a facilitating acid temperatureadjustment delay period or a facilitating acid holding delay period. Forexample, a first facilitating acid temperature adjustment delay periodis the amount of time after one or more facilitating acids is added andprior to the addition of the next ingredient (or portion thereof) thatit takes to heat the mixture to a temperature or range of temperatures(the first facilitating acid temperature). A first facilitating acidholding delay period is the amount of time the mixture is held at thefirst facilitating acid temperature (which may be ambient temperature)before being heated or cooled to another temperature or before addingthe next ingredient or next portion of a facilitating acid. A secondfacilitating acid temperature adjustment delay period is the amount oftime after the first holding delay period that it takes to heat or coolthe mixture to another temperature or temperature range (the secondfacilitating acid temperature). A second facilitating acid holding delayperiod is the amount of time the mixture is held at the secondfacilitating acid temperature before being heated or cooled to anothertemperature or before adding the next ingredient. Additionalfacilitating acid temperature adjustment delay periods or facilitatingacid holding delay periods (i.e. a third facilitating acid temperatureadjustment delay period) follow the same pattern. Generally, theduration of each facilitating acid temperature adjustment delay periodwill be about 30 minutes to 24 hours, or more typically about 30 minutesto 5 hours. However, the duration of any facilitating acid temperatureadjustment delay period will vary depending on the size of the greasebatch, the equipment used to mix and heat the batch, and the temperaturedifferential between the starting temperature and final temperature, aswill be understood by those of ordinary skill in the art.

Most preferably, a facilitating acid delay period occurs between theaddition of a facilitating acid and the addition of magnesium sulfonate,calcium hydroxyapatite, or calcium carbonate (as the next subsequentlyadded ingredient). Other ingredients may also serve at the nextsubsequently added ingredient following a facilitating acid delay.According to another preferred embodiment, water as a converting agentis not present in a mixture of other ingredients during a facilitatingacid delay period. Most preferably, water is not added as the nextsubsequent ingredient after a facilitating acid delay period, but isadded sometime after the next subsequent ingredient.

According to another preferred embodiment, a simultaneous facilitatingacid delay and a magnesium sulfonate delay are used. In this embodiment,there is no magnesium sulfonate present when the facilitating acid isadded to an initial mixture of overbased calcium sulfonate and base oil.The initial mixture of base oil, overbased calcium sulfonate, andfacilitating acid are sufficiently mixed to allow the facilitating acidto react with the overbased calcium sulfonate prior to adding anymagnesium sulfonate. After this delay period, which is both afacilitating acid delay period and a magnesium sulfonate delay period,at least a portion of the magnesium sulfonate is added. The varioustypes and combinations of delays previously described are equallyapplicable in this embodiment regarding the delay or delays between theaddition of the facilitating acid and the addition of the magnesiumsulfonate. If the magnesium sulfonate that is added is only the first oftwo portions of magnesium sulfonate to be added, with the second portionbeing added later, then a split magnesium sulfonate addition methodwould also be employed, as previously discussed. Most preferably, when afacilitating acid delay and magnesium sulfonate delay are simultaneous,water is not added as a converting agent until after at least the firstportion (or all) of the magnesium sulfonate is added. The importance ofthis specific combined use of the delayed facilitating acid method andthe delayed magnesium sulfonate method is that such a combined use ofthese methods allows the facilitating acid to react with the calciumsulfonate, but not with the magnesium sulfonate. The delay between theaddition of the facilitating acid and the first portion of the magnesiumsulfonate may be 20-30 minutes, or longer. A shorter delay, such as 20minutes, would still qualify as a true delay period herein, even withoutany temperature adjustment. This is because the reaction of facilitatingacid with the calcium sulfonate (or magnesium sulfonate, if a portion ofthe magnesium sulfonate is added prior to the facilitating acidaccording to another preferred embodiment) will typically be veryfacile, and will be expected to occur rapidly upon mixing, even atnormal ambient temperatures. Any intentional delay between the additionof the facilitating acid and a first portion (or all) of the magnesiumsulfonate as herein described that sufficiently allows reaction of thefacilitating acid with the already present calcium sulfonate qualifiesas a facilitating acid delay period and a magnesium sulfonate delayperiod.

A short delay (20 minutes or less) for mixing without heating betweenthe addition of the facilitating acid and calcium hydroxyapatite (orcalcium carbonate) is not considered a facilitating acid holding delayperiod because the calcium hydroxyapatite (the next added ingredient) isconsidered non-reactive with the facilitating acid. If the next addedingredient were considered reactive (such a magnesium sulfonate), then ashort mixing time without heating would be a facilitating acid holdingdelay period. Additionally, if the short mixing time of 20 minutesinvolved heating or was a longer mixing time, it would be considered afacilitating acid delay period regardless of which ingredient is thenext added ingredient.

Methods for Adding Calcium Containing Bases

According to several preferred embodiments, the step(s) of adding one ormore calcium containing base(s)) involves one of the following: (a)admixing finely divided calcium hydroxyapatite prior to conversion asthe only calcium containing base added; (b) admixing finely dividedcalcium hydroxyapatite and calcium carbonate in an amount sufficient tofully react with and neutralize subsequently added complexing acids,according to one embodiment; (c) admixing finely divided calciumhydroxyapatite and calcium hydroxide and/or calcium oxide in an amountsufficient to fully react with and neutralize subsequently addedcomplexing acids, with the added calcium hydroxide and/or calcium oxidepreferably being present in an amount not more than 90% of the hydroxideequivalent basicity provided by the total of the added calcium hydroxideand/or calcium oxide and the calcium hydroxyapatite, according toanother embodiment of the invention; (d) admixing added calciumcarbonate after conversion, according to another embodiment of theinvention; (e) admixing calcium hydroxyapatite after conversion and inan amount sufficient to completely react with and neutralize anycomplexing acids added post-conversion, according to yet anotherembodiment of the invention; (f) admixing finely divided calciumcarbonate as an oil-insoluble solid calcium-containing base prior toconversion and admixing finely divided calcium hydroxyapatite andcalcium hydroxide and/or calcium oxide in an amount insufficient tofully react with and neutralize subsequently added complexing acids,with the added calcium hydroxide and/or calcium oxide preferably beingpresent in an amount not more than 90% of the hydroxide equivalentbasicity provided by the total of the added calcium hydroxide and/orcalcium oxide and the calcium hydroxyapatite, with the previously addedcalcium carbonate being added in an amount sufficient to fully reactwith and neutralize the portion of any subsequently added complexingacids not neutralized by the calcium hydroxyapatite and calciumhydroxide and/or calcium oxide.

Added Alkali Metal Hydroxide Methods

According to yet another preferred embodiment, a calcium magnesiumsulfonate grease is made with added alkali metal hydroxide. The alkalimetal hydroxide is preferably dissolved in water and the solution addedto the other ingredients. According to other preferred embodiments, whenan alkali metal hydroxide is added, one or more of the following stepsare included: (a) alkali metal hydroxide is dissolved in the water to beadded as a converting agent and the water with dissolved alkali metalhydroxide is added all at once prior to conversion (with additionalwater added later in the process to make-up for evaporative losses, asneeded); (b) (i) a first portion of water is added as a converting agentprior to conversion and a second portion of water is added afterconversion and (ii) the alkali metal hydroxide is dissolved in the firstportion of water or the second portion of water or both; (c) water isadded in at least two separate pre-conversion steps as a convertingagent, with one or more temperature adjustment steps, addition ofanother ingredient(s) steps or a combination thereof between the firstaddition of water as a converting agent and the second addition of wateras a converting agent, and the alkali metal hydroxide is dissolved inthe initial or first addition of water as a converting agent, or thesecond or subsequent addition of water as a converting agent, or both;(d) at least part of the complexing acids are added prior to heating;(e) all of the complexing acid(s) are added prior to heating; (f) whenadded calcium carbonate is used as the added calcium containing base forreacting with complexing acids, it added before any complexing acid(s);(g) calcium hydroxyapatite, added calcium hydroxide and added calciumcarbonate are all used as calcium containing bases for reacting withcomplexing acids; (h) the water with dissolved alkali metal hydroxide isadded after the calcium containing base(s) are added and/or after aportion of the pre-conversion complexing acid(s) are added; and/or (i)the water with dissolved alkali metal hydroxide (or alkali metalhydroxide added separately) are added before adding a least a portion ofone or more complexing acids. These embodiments may be combined with anycalcium base addition method, the converting agent delay method, theaddition of magnesium sulfonate (all at one, with a split magnesiumsulfonate addition method, a magnesium sulfonate delayed method, or anycombination thereof), or any combination thereof.

The preferred embodiments of the methods herein may occur in either anopen or closed kettle as is commonly used for grease manufacturing. Theconversion process can be achieved at normal atmospheric pressure orunder pressure in a closed kettle. Manufacturing in open kettles(vessels not under pressure) is preferred since such greasemanufacturing equipment is commonly available. For the purposes of thisinvention an open vessel is any vessel with or without a top cover orhatch as long as any such top cover or hatch is not vapor-tight so thatsignificant pressure cannot be generated during heating. Using such anopen vessel with the top cover or hatch closed during the conversionprocess will help to retain the necessary level of water as a convertingagent while generally allowing a conversion temperature at or even abovethe boiling point of water. Such higher conversion temperatures canresult in further thickener yield improvements for both simple andcomplex calcium sulfonate greases, as will be understood by those withordinary skill in the art. Manufacturing in pressurized kettles may alsobe used and may result in even greater improvement in thickener yield,but the pressurized processes may be more complicated and difficult tocontrol. Additionally, manufacturing calcium magnesium sulfonate greasesin pressurized kettles may result in productivity issues. The use ofpressurized reactions can be important for certain types of greases(such as polyurea greases) and most grease plants will only have alimited number of pressurized kettles available. Using a pressurizedkettle to make calcium magnesium sulfonate greases, where pressurizedreactions are not as important, may limit a plant's ability to makeother greases where those reactions are important. These issues areavoided with open vessels.

The overbased calcium magnesium sulfonate grease compositions withoutconventional non-aqueous converting agents and methods for making suchcompositions according to various embodiments the invention are furtherdescribed and explained in relation to the following examples. Theoverbased calcium sulfonate used in Examples 1, 3, and 6-13 was a goodquality overbased calcium sulfonate. The overbased calcium sulfonateused in all other examples was a poor quality calcium sulfonate similarto that used in Examples 10 and 11 of the '406 patent.

Example 1

(Baseline Example—Non-Aqueous Converting Agent Used) A calcium magnesiumsulfonate complex grease was made based on the calcium carbonate-basedcalcium sulfonate grease technology of the '265 patent and the calciummagnesium sulfonate grease technology of the '792 application. The ratioof overbased calcium sulfonate to overbased magnesium sulfonate wasabout 90/10. A converting agent delay method, where there was a delaybetween the addition of water as a converting agent and the addition ofa non-aqueous converting agent, as described in U.S. application Ser.No. 14/990,473 (incorporated herein by reference), was also used. Allthe overbased magnesium sulfonate was added at the beginning.

The grease was made as follows: 310.14 grams of 400 TBN overbasedoil-soluble calcium sulfonate were added to an open mixing vesselfollowed by 345.89 grams of a solvent neutral group 1 paraffinic baseoil having a viscosity of about 600 SUS at 100 F. The 400 TBN overbasedoil-soluble calcium sulfonate was a good quality calcium. Mixing withoutheat began using a planetary mixing paddle. Then 31.60 grams ofoverbased magnesium sulfonate A was added and allowed to mix in for 15minutes. Then 31.20 grams of a primarily C12 alkylbenzene sulfonic acidwere added. After mixing for 20 minutes, 75.12 grams of finely dividedcalcium carbonate with a mean particle size below 5 microns were addedand allowed to mix in for 20 minutes. Then 0.84 grams of glacial aceticacid and 8.18 grams of 12-hydroxystearic acid were added. The mixturewas stirred for 10 minutes. Then 40.08 grams water were added, and themixture was heated with continued mixing to a temperature of 190 F to200 F. This represents a temperature adjustment delay. The mixture wasmixed at this temperature range for 30 minutes. This represents aholding delay. During that time, significant thickening had occurred,with a grease structure having formed.

Fourier Transform Infrared (FTIR) spectroscopy indicated that water wasbeing lost due to evaporation. Another 70 ml water were added. FTIRspectroscopy also indicated that conversion had partially occurred eventhough no hexylene glycol (non-aqueous converting agent) had yet beenadded. After the 30 minutes holding delay at 190 to 200 F, 15.76 gramsof hexylene glycol (a conventional non-aqueous converting agent) wereadded. Shortly after this, FTIR spectroscopy indicating that theconversion of the amorphous calcium carbonate to crystalline calciumcarbonate (calcite) had occurred. However, the batch seemed to softensomewhat after the glycol was added. Another 20 ml water were addedfollowed by 2.57 grams of glacial acetic acid and 16.36 grams of12-hydroxystearic acid. These two complexing acids were allowed to reactfor 10 minutes. Then 16.60 grams of a 75% solution of phosphoric acid inwater were slowly added and allowed to mix in and react.

The grease was then heated to 390 to 400 F. As the mixture was heated,the grease continued to become increasingly thin and fluid. The heatingmantle was removed from the mixer and the grease was allowed to coolwhile continuing to be mixed. The mixture was very thin and had verylittle if any significant grease texture. When the temperature was below170 F, a sample was removed from the mixer and given passes through athree-roll mill. The milled grease had an unworked penetration of 189.This result was extremely surprising and indicated that a very unusualand highly rheopectic structure had formed. Three more portions of thesame base oil totaling 116.02 grams were added. The grease was thenremoved from the mixer and given three passes through a three-roll millto achieve a final smooth homogenous texture. The grease had a worked 60stroke penetration of 290. The percent overbased oil-soluble calciumsulfonate in the final grease was 31.96%. The dropping point was 617 F.Before milling, this Example 1 grease had an extremely fluid texture.This very unusual property could have multiple applications where a veryfluid and pumpable lubricant is needed until it is delivered to theequipment to be lubricated. If either the equipment dispensing thelubricant to the equipment or the equipment itself (or both) canadequately shear the lubricant so as to simulate milling, then a firmgrease could be generated. The advantage of such a lubricant is that itwould have the pumpability and mobility of a fluid but the texture of agrease in the equipment to be lubricated.

Example 2

(Baseline Example—Non-Aqueous Converting Agent Used) Another grease wasmade similar to the previous Example 1 grease. However, there were somedifferences. First, this grease used a poor quality overbased calciumsulfonate, as described in the '406 patent. Second, the overbasedmagnesium sulfonate was intentionally not added until the initial baseoil, overbased calcium sulfonate, and facilitating acid had been addedand mixed for 20 minutes without any applied heat (a simultaneousfacilitating acid delay period and magnesium sulfonate delay period).Third, this grease used a 16.52 gram addition of a 75% solution ofphosphoric acid in water similar to the Example 1 grease. The finalmilled Example 2 grease had a worked 60 stroke penetration of 293. Thepercent overbased oil-soluble calcium sulfonate in the final grease was26.78%. However, the dropping point was 520 F. It should be noted thatthis grease had a composition that was essentially the same as thegreases of Examples 6-9 of the '406 patent. Those four greases also usedthe same poor quality overbased calcium sulfonate. The dropping pointsof those four greases were 496, 483, 490, and 509; the average value was495 F. Although the dropping point of this Example 2 grease was low, itwas somewhat higher than those four greases from the '406 patent.

Example 3

A grease was made similar to the previous Example 1 grease. Like theExample 1 grease, this grease had a ratio of overbased calcium sulfonateto overbased magnesium sulfonate that was about 90/10. All the overbasedmagnesium sulfonate was added at the beginning along with the overbasedcalcium sulfonate, before the facilitating acid was added. This Example3 grease used the same good quality overbased calcium sulfonate as theExample 1 grease. The only significant difference between this greaseand the Example 1 grease was that this grease did not have anyconventional non-aqueous converting agent added. Water was added as theonly conventional converting agent and additional water was added asrequired to replace any water lost due to evaporation during theconversion process. Conversion was monitored by FTIR spectra and took 2hours to complete. The conversion took place due only to water, theoverbased magnesium sulfonate, and any effects due to the initialamounts of the pre-conversion complexing acids that were added. As thegrease was heated to its top temperature, it significantly softened in amanner similar to the Example 1 grease. The grease texture was recoveredupon milling, just as was observed in the Example 1 grease. This extremerheopectic property has the same potential utility as mentioned inExample 1.

Example 4

Another grease was made similar to previous Example 3 grease. The onlysignificant difference was that a poor quality overbased calciumsulfonate was used. Conversion was monitored by FTIR spectra and took 7hours to complete.

Example 5

Another grease was made similar to previous Example 4 grease. The onlysignificant difference was that only about half the amount of overbasedmagnesium sulfonate was used. This grease used the same poor qualityoverbased calcium sulfonate as was used in previous examples of thisdocument. Conversion was monitored by FTIR spectra and took 10.5 hoursto complete. A summary of the Example 3-5 greases are provided below inTable 4.

TABLE 4 Summary of Examples 3-5 Example 3 4 5 % Overbased CalciumSulfonate 32.77 37.05 34.49 % Overbased Magnesium 3.47 3.72 1.68Sulfonate Quality of Calcium Sulfonate Good Poor Poor Ratio of CaSulfonate to Mg 90/10 90/10 95/5 Sulfonate Time to Conversion, hrs 2 710.5 Unworked Penetration 280 289 267 Worked Penetration 292 295 295Dropping Point, F. >650 558 562 Four Ball EP, Weld Load, kg 500 500 NDFour Ball Wear 0.37 0.37 0.38 Roll Stability at 25 C., 2 hrs: Initialworked Penetration 269 295 295 Final Worked Penetration 267 317 303 %Change −0.7 7.5 2.7 Dropping Pt After Test, F. 633 520 522 RollStability at 150 C., 2 hrs: Initial worked Penetration 269 295 295 FinalWorked Penetration 281 301 291 % Change 4.5 2 −1.4 Dropping Pt AfterTest, F. >650 583 574

Except for the omission of a conventional non-aqueous converting agentand the addition of overbased magnesium sulfonate, the Example 3-5greases had essentially the same composition as the greases of Examples6-9 of the '406 patent (which used hexylene glycol and water asconventional converting agents). The Example 6-9 greases of the '406patent used the same poor quality overbased calcium sulfonate as theExample 4 and 5 greases herein. The only compositional difference wasthat the Example 4-5 greases contained overbased magnesium sulfonate anddid not include the hexylene glycol. Although the dropping points of theExample 4 and 5 greases (which contained the poor quality overbasedcalcium sulfonate) were rather low, they were much improved over theExamples 6-9 greases of the '406 patent (which also contained the samepoor quality overbased calcium sulfonate and had dropping points rangingfrom 483 F-509 F). It appears that the addition of magnesium sulfonateacts as a converting agent, so that the addition of a conventionalnon-aqueous converting agent is not required. The conversion process didtake much longer when poor instead of good quality overbased calciumsulfonate was used. However, the beneficial effect of the overbasedmagnesium sulfonate on conversion was apparent by comparing the requiredconversion times for Example 4 and 5. When the concentration ofoverbased magnesium sulfonate was significantly reduced, the conversiontime significantly increased. This shows that the overbased magnesiumsulfonate is having a positive effect on conversion. Also, the droppingpoint of both Example 4 and 5 greases improved after being sheared at150 C, as indicated by the roll stability test data. This again showsthe potential beneficial effect of overbased magnesium sulfonate onimproving high temperature structural stability when used at highertemperatures.

Another important observation is made by comparing the dropping point ofthe Example 2 grease with the Example 4 and 5 greases. All three greaseswere compositionally similar. They all contained the same poor qualityoverbased calcium sulfonate and the same overbased magnesium sulfonate.They also contained the same complexing acids added in a similar way.There was only one significant compositional difference: the Example 2grease contained a conventional non-aqueous converting agent (hexyleneglycol) whereas the Example 4 and 5 greases did not. Yet, the droppingpoints of the Example 4 and 5 greases were significantly higher thanthat of the Example 2 grease. This demonstrates that when a calciummagnesium sulfonate complex grease is made without a conventionalnon-aqueous converting agent, a higher dropping point is possiblecompared to a similar grease made with a conventional non-aqueousconverting agent. This result is a surprising and unexpected benefit ofusing overbased magnesium sulfonates in these greases, and it was notexpected based on the teachings of the prior art.

Example 6

Another grease was made similar to the previous Example 3 grease.However, a significant difference was that a facilitating acid delaymethod was used. Specifically, the facilitating acid was added after theinitial base oil portion and the overbased calcium sulfonate was added.The facilitating acid was allowed to mix with these components for 30minutes at ambient temperature before adding the next reactivecomponent—the overbased magnesium sulfonate (this is a simultaneousfacilitating acid delay period and magnesium sulfonate delay period asdescribed in the '839 application). Also, a second amount of powderedcalcium carbonate was added post-conversion and a higher amount of12-hydroxystearic acid was added thereafter. Finally, this example wasfinished so that it was an NLGI No. 1 grade grease.

The grease was made as follows: 310.35 grams of 400 TBN overbasedoil-soluble calcium sulfonate were added to an open mixing vesselfollowed by 345.38 grams of a solvent neutral group 1 paraffinic baseoil having a viscosity of about 600 SUS at 100 F. The 400 TBN overbasedoil-soluble calcium sulfonate was a good quality calcium sulfonate asdefined by our recently issued U.S. Pat. No. 9,458,406. Mixing withoutheat began using a planetary mixing paddle. Then 31.03 grams of aprimarily C12 alkylbenzene sulfonic acid were added. After mixing for 30minutes, 31.18 grams of overbased magnesium sulfonate A was added andallowed to mix in for 15 minutes (a facilitating acid delay period and amagnesium sulfonate delay period). Then 75.25 grams of finely dividedcalcium carbonate with a mean particle size below 5 microns were addedand allowed to mix in for 20 minutes. Then 0.87 grams of glacial aceticacid and 8.09 grams of 12-hydroxystearic acid were added. The mixturewas stirred for 10 minutes. Then 40.0 grams water were added, and themixture was heated with continued mixing to a temperature of 190 F to200 F. As the mixture reached 181 F it was showing visible signs ofthickening. After one hour and 30 minutes, FTIR spectroscopy indicatedthat the conversion of the amorphous calcium carbonate to crystallinecalcium carbonate had occurred. During that time, two 40 ml portions ofwater were added to replace water lost due to evaporation. Another 25.05grams of the same powdered calcium carbonate were added and allowed tomix for 20 minutes.

Then 1.53 grams of glacial acetic acid and 41.97 grams of12-hydroxystearic acid were added. These two complexing acids wereallowed to react for 30 minutes. Then 16.90 grams of a 75% solution ofphosphoric acid in water were slowly added and allowed to mix in andreact. The grease was then heated to 340 F. The grease retained itsgrease consistency during the heating to top temperature. The heatingmantle was removed from the mixer and the grease was allowed to coolwhile continuing to be mixed. When the temperature was below 170 F, asample was removed from the mixer and given three passes through athree-roll mill. The milled grease had an unworked penetration of 192.Three more portions of the same paraffinic base oil totaling 125.29grams were added. The grease was then removed from the mixer and giventhree passes through a three-roll mill to achieve a final smoothhomogenous texture. The grease had a worked 60 stroke penetration of326, an NLGI No. 1 grade product. The percent overbased oil-solublecalcium sulfonate in the final grease was 30.64%. The dropping point was619 F.

Example 7

Another grease was made similar to the previous Example 6 grease. Likethe previous Examples, this calcium sulfonate complex grease was madebased on the calcium carbonate-based calcium sulfonate grease technologyof the '265 patent. Like the previous Example 6 grease, the ratio ofoverbased calcium sulfonate to overbased magnesium sulfonate was about90/10. Also, a facilitating acid delay method was used. Specifically,the facilitating acid was added after the initial base oil portion andthe overbased calcium sulfonate was added. The facilitating acid wasallowed to mix with these components for 30 minutes at ambienttemperature before adding the next reactive component—the overbasedmagnesium sulfonate. All the overbased magnesium sulfonate was added atthat time. The only significant differences between this grease and theprevious Example 6 grease were as follows: this grease had a highertotal amount of the powdered calcium carbonate added with equal portionsadded before and after conversion; a higher amount of 12-hydroxystearicacid was added after conversion; powdered anhydrous calcium sulfate wasadded after the grease had been heated to top temperature; and the batchsize was increased to allow better mixing during the early part of thebatch.

The grease was made as follows: 372.10 grams of 400 TBN overbasedoil-soluble calcium sulfonate were added to an open mixing vesselfollowed by 316.03 grams of a solvent neutral group 1 paraffinic baseoil having a viscosity of about 600 SUS at 100 F. The 400 TBN overbasedoil-soluble calcium sulfonate was a good quality calcium sulfonate asdefined in the '406 patent. Mixing without heat began using a planetarymixing paddle. Then 37.47 grams of a primarily C12 alkylbenzene sulfonicacid were added. After mixing for 30 minutes, 37.29 grams of overbasedmagnesium sulfonate A (the same commercial source used in severalexamples described in the '792 application) was added and allowed to mixin for 15 minutes. This represents a facilitating acid delay period anda magnesium sulfonate delay period. Then 90.11 grams of finely dividedcalcium carbonate with a mean particle size below 5 microns were addedand allowed to mix in for 20 minutes. Then 1.01 grams of glacial aceticacid and 9.25 grams of 12-hydroxystearic acid were added. The mixturewas stirred for 10 minutes. Then 48.14 grams water were added, and themixture was heated with continued mixing to a temperature of 190 F to200 F. As the mixture reached 170 F it was showing visible signs ofthickening. After one hour and 30 minutes, FTIR spectroscopy indicatedthat the conversion of the amorphous calcium carbonate to crystallinecalcium carbonate had occurred. During that time, two 30 ml portions ofwater were added to replace water lost due to evaporation. Also, another19.70 grams of the same paraffinic base oil was added due to theincreasing thickness of the grease.

After conversion was considered complete, another 90.17 grams of thesame powdered calcium carbonate were added and allowed to mix for 20minutes. Then 1.88 grams of glacial acetic acid and 86.75 grams of12-hydroxystearic acid were added. These two complexing acids wereallowed to react for 30 minutes. Another 39.87 grams of the sameparaffinic base oil was added. Then 19.89 grams of a 75% solution ofphosphoric acid in water were slowly added and allowed to mix in andreact. The grease was then heated to 340 F. The grease retained itsgrease consistency during the heating to top temperature. The heatingmantle was removed from the mixer and the grease was allowed to coolwhile continuing to be mixed. When the grease had cooled to below 300 F,60.14 grams of food grade anhydrous calcium sulfate having a meanparticle size below 5 microns were added. When the temperature was below170 F, a sample was removed from the mixer and given three passesthrough a three-roll mill. The milled grease had an unworked penetrationof 189. Six more portions of the same paraffinic base oil totaling244.17 grams were added. The grease was then removed from the mixer andgiven three passes through a three-roll mill to achieve a final smoothhomogenous texture. The grease had a worked 60 stroke penetration of256. The percent overbased oil-soluble calcium sulfonate in the finalgrease was 26.10%. Using the customary inverse linear relationshipbetween worked penetration and percent overbased calcium sulfonateconcentration, this example grease would have had a percent overbasedcalcium sulfonate concentration of 23.9% if additional base oil had beenadded to bring the worked penetration to a value of 280 (the center ofthe NLGI No. 2 grade range). The dropping point was 646 F. It should benoted that this Example 7 grease had a thickener yield that was superiorto any other calcium carbonate-based calcium magnesium sulfonate complexgrease described in the '792 application, where a conventionalnon-aqueous converting agent was used. Furthermore, this Example 7grease had a thickener yield that was superior to any grease describedin the '265 patent. This excellent thickener yield was obtained whilemaintaining a very high dropping point. This shows the surprising andunexpected benefit of using an overbased magnesium sulfonate without anyconventional non-aqueous converting agent when making a calciummagnesium sulfonate complex greases.

A series of six grease examples were prepared to examine the ability ofoverbased magnesium sulfonate to act as a new, non-conventionalconverting agent in place of a conventional non-aqueous convertingagents when making calcium magnesium sulfonate greases with addedcalcium hydroxyapatite as a calcium containing base for reacting withcomplexing acids.

Example 8

A grease similar to Example 3 grease was made. The only significantdifference was that a portion of calcium hydroxyapatite was added afterthe initial portion of base oil, the overbased calcium and magnesiumsulfonates, and the facilitating acid. None of the preferred delaymethods were used in making this grease. Also, the weight/weight ratioof overbased calcium sulfonate to overbased magnesium sulfonate wasabout 90/10.

The grease was made as follows: 310.06 grams of 400 TBN overbasedoil-soluble calcium sulfonate and 31.16 grams of overbased magnesiumsulfonate A were added to an open mixing vessel followed by 345.96 gramsof a solvent neutral group 1 paraffinic base oil having a viscosity ofabout 600 SUS at 100 F. The 400 TBN overbased oil-soluble calciumsulfonate was a good quality calcium sulfonate according to the '406patent. Mixing without heat began using a planetary mixing paddle. Then31.14 grams of a primarily C12 alkylbenzene sulfonic acid were added.After mixing for 20 minutes, 10.02 grams of calcium hydroxyapatite witha mean particle size below 5 microns were added and allowed to mix infor 5 minutes. Then 75.08 grams of finely divided calcium carbonate witha mean particle size below 5 microns were added and allowed to mix infor 20 minutes. Then 0.91 grams of glacial acetic acid and 8.12 grams of12-hydroxystearic acid were added. The mixture was stirred for 10minutes. Then 40.15 grams water (as the only conventional convertingagent added) were added, and the mixture was heated with continuedmixing to a temperature of 190 F to 200 F. As the mixture reached 190 Fit was showing visible signs of thickening. After one hour and 40minutes, FTIR spectroscopy indicated that the conversion of theamorphous calcium carbonate to crystalline calcium carbonate hadoccurred. During that time, two 20 ml portions of water were added toreplace water lost due to evaporation.

Then 1.42 grams of glacial acetic acid and 17.40 grams of12-hydroxystearic acid were added. These two complexing acids wereallowed to react for 30 minutes. Then 17.07 grams of a 75% solution ofphosphoric acid in water were slowly added and allowed to mix in andreact. The grease was then heated to 390-400 F. The grease lost nearlyall its grease consistency as it began to be heated to the toptemperature. This thinned out texture was retained until the grease wasmilled. This is similar to the behavior observed in the both the Example1 grease (which used a conventional non-aqueous converting agent) andthe Example 3 grease (which did not use a conventional non-aqueousconverting agent). The heating mantle was removed from the mixer and thegrease was allowed to cool while continuing to be mixed. When thetemperature was below 170 F, a sample was removed from the mixer andgiven three passes through a three-roll mill. The milled grease had anunworked penetration of 189. Two more portions of the same paraffinicbase oil totaling 100.54 grams were added. The grease was then removedfrom the mixer and given three passes through a three-roll mill toachieve a final smooth homogenous texture. The grease had a worked 60stroke penetration of 273. The percent overbased oil-soluble calciumsulfonate in the final grease was 32.68%. The dropping point was 614 F.It should be noted that in this grease, like the Example 1 and 3greases, the magnesium sulfonate was added at the beginning prior toadding the facilitating acid. This allowed the facilitating acid to mixand react with both the calcium sulfonate and magnesium sulfonate.Interestingly, all these greases also exhibited marked thinning out asthey were heated to top temperature, and they recovered their greaseconsistency only when milled.

Example 9

Another grease was made similar to the previous Example 8 grease. Therewere only two significant differences: first, the amount of calciumhydroxyapatite was essentially doubled, being increased from 10.02 gramsto 20.62; second, the grease was heated to a top temperature of 340 Finstead of 390-400 F. It was observed that this grease visibly convertedto a grease much more quickly than the Example 8 grease. Also, thisgrease did not begin to thin out until it reached 330 F, and it thinnedout significantly less during the rest of the process compared to theExample 8 grease. The final milled grease had a worked 60 strokepenetration of 291. The percent overbased oil-soluble calcium sulfonatein the final grease was 29.65%. The dropping point was 622 F.

Example 10

Another grease was made similar to the previous Example 9 grease. Theonly significant difference was that the amount of calciumhydroxyapatite was again nearly doubled, being increased from 20.62grams to 40.12 grams. It was observed that this grease visibly convertedto a grease almost as soon as it reached 190 F. Also, this grease didnot thin out as much as the previous two greases when it was heated to340 F. Although it softened somewhat, it retained a distinct greasestructure. The final milled grease had a worked 60 stroke penetration of285. The percent overbased oil-soluble calcium sulfonate in the finalgrease was 30.43%. The dropping point was 621 F.

Example 11

Another grease was made similar to the previous Example 10 grease. Theonly significant difference was that the amount of overbased magnesiumsulfonate was cut in half. The weight/weight ratio of overbased calciumsulfonate to overbased magnesium sulfonate was about 95/5. It wasobserved that conversion to a grease took much longer for this Examplecompared to the previous Example. This grease required about 30 minutesof mixing at 190-200 F to visibly convert to a grease. However, thisgrease retained its grease structure all the way through the process ofmaking it. The final milled grease had a worked 60 stroke penetration of289. The percent overbased oil-soluble calcium sulfonate in the finalgrease was 29.69%. The dropping point was 635 F. By comparing theresults of the Example 8-11 greases it appears that once again theoverbased magnesium sulfonate is acting as a new, non-conventionalconverting agent and that the use of a conventional non-aqueousconverting agent is not needed. When the magnesium sulfonateconcentration was significantly reduced (Example 11 compared to Example10) conversion took significantly longer. Also, it appears that thepresence of calcium hydroxyapatite added before conversion has an effectof reducing the thinning out effect that otherwise occurs when suchcalcium-magnesium sulfonate greases are made.

The next two example greases explore what happens when a delayedmagnesium sulfonate addition method is used in a grease that also usedcalcium hydroxyapatite and omitted any conventional non-aqueousconverting agent.

Example 12

A grease was made similar to the previous Example 11 grease. The onlysignificant difference was that the overbased magnesium sulfonate wasnot added until the unconverted mixture had been heated to 190-200 F (amagnesium sulfonate temperature adjustment delay period) and held atthat temperature for 30 minutes (a magnesium sulfonate holding delayperiod).

The grease was made as follows: 310.09 grams of 400 TBN overbasedoil-soluble calcium sulfonate was added to an open mixing vesselfollowed by 340.03 grams of a solvent neutral group 1 paraffinic baseoil having a viscosity of about 600 SUS at 100 F. The 400 TBN overbasedoil-soluble calcium sulfonate was a good quality calcium sulfonate asdefined in the '406 patent. Mixing without heat began using a planetarymixing paddle. Then 31.10 grams of a primarily C12 alkylbenzene sulfonicacid were added. After mixing for 20 minutes, 40.16 grams of calciumhydroxyapatite with a mean particle size below 5 microns were added andallowed to mix in for 5 minutes. It should be noted that the 20 mixingdelay without heat between the addition of a facilitating acid and thenext ingredient in this example and Examples 8-11 do not constitute afacilitating acid delay method as described in the '839 application.This is because the next ingredient added after the facilitating acid iscalcium hydroxyapatite, which is not significantly reactive towards thefacilitating acid, as shown in the '406 patent. Then 75.23 grams offinely divided calcium carbonate with a mean particle size below 5microns were added and allowed to mix in for 20 minutes. Then 0.89 gramsof glacial acetic acid and 8.11 grams of 12-hydroxystearic acid wereadded. The mixture was stirred for 10 minutes. Then 40.45 grams waterwere added, and the mixture was heated with continued mixing to atemperature of 190 F to 200 F. The mixture was held at that temperaturerange for 30 minutes during which time it began to thicken to a grease.During the 30 minutes, another 40.2 grams water was added to replacewater lost due to evaporation. After the 30 minutes, 16.21 grams ofoverbased magnesium sulfonate A was added.

After one hour, FTIR spectroscopy indicated that the conversion of theamorphous calcium carbonate to crystalline calcium carbonate hadoccurred. During that time, two 40 ml portions of water were added toreplace water lost due to evaporation. Then 1.53 grams of glacial aceticacid and 16.41 grams of 12-hydroxystearic acid were added. These twocomplexing acids were allowed to react for 30 minutes. During that timeanother 49.50 grams of the same paraffinic base oil was added as thegrease continued to thicken. Towards the end of the 30 minutes ofmixing, the temperature of the grease increased to about 240 F, Theheating mantle was removed and the batch was allowed to cool to 200 F.Then 17.28 grams of a 75% solution of phosphoric acid in water wereslowly added and allowed to mix in and react. The grease was then heatedto 340 F. The grease retained all its grease consistency during theentire heating process. The heating mantle was removed from the mixerand the grease was allowed to cool while continuing to be mixed. Whenthe temperature was below 160 F, three more portions of the sameparaffinic base oil totaling 132.07 grams were added. The grease wasthen removed from the mixer and given three passes through a three-rollmill to achieve a final smooth homogenous texture. The grease had aworked 60 stroke penetration of 287. The percent overbased oil-solublecalcium sulfonate in the final grease was 29.86%. The dropping pointwas >650 F.

Example 13

Another grease was made similar to the previous Example 12 grease.However, there were several important differences. After the initialbase oil, overbased calcium sulfonate, and facilitating acid were addedand mixed, heating to 190-200 F began (since the mixture was heated,this is a facilitating acid temperature adjustment delay). Only whenthis temperature range was reached were the calcium hydroxyapatite andpowdered calcium carbonate added and allowed to mix for 30 minutes. Thenthe initial portions of 12-hydroxystearic acid and acetic acid wereadded and allowed to react in the normal expected way for 30 minutesbefore adding the water. Once the water was added, there was another 3hour and 40 minute delay before adding the overbased magnesium sulfonate(a magnesium sulfonate delayed period). Since the calcium hydroxyapatiteand powdered calcium carbonate would likely not react significantly withthe facilitating acid (given what has been previously disclosed in the'406 patent), there would be additional facilitating acid delay holdingdelay periods after the facilitating acid temperature adjustment delayuntil the overbased magnesium sulfonate was added (as the next addedingredient that is reactive with the facilitating acid). This Example 13grease also differed from the previous Example 12 grease in that afterconversion was complete, some powdered calcium hydroxide was added. Thepost-conversion amount of 12-hydroxystearic acid was increased, andboric acid was added as a post-conversion complexing acid. Finally,anhydrous calcium sulfate and a small amount of an antioxidant wereadded as the grease was cooled down from its top temperature.

The grease was made as follows: 310.02 grams of 400 TBN overbasedoil-soluble calcium sulfonate was added to an open mixing vesselfollowed by 345.83 grams of a solvent neutral group 1 paraffinic baseoil having a viscosity of about 600 SUS at 100 F. The 400 TBN overbasedoil-soluble calcium sulfonate was a good quality calcium sulfonate asdefined in the '406 patent. Mixing without heat began using a planetarymixing paddle. Then 31.04 grams of a primarily C12 alkylbenzene sulfonicacid were added. The mixture was then heated to 190-200 F (afacilitating acid temperature adjustment delay period). Once thistemperature range was reached, 40.23 grams of calcium hydroxyapatitewith a mean particle size below 5 microns were added followed by 75.04grams of finely divided calcium carbonate with a mean particle sizebelow 5 microns were added and allowed to mix in for 30 minutes. Then0.88 grams of glacial acetic acid and 8.10 grams of 12-hydroxystearicacid were added. The mixture was stirred for 30 minutes to allowreaction of the two complexing acids. Then 40.26 grams water were added,and the mixing continued at the 190-200 F temperature range. After onehour of mixing, the batch began to visibly change to a grease. Themixture was stirred for another 2 hours and 40 minutes during which timefour portions of 40 ml water was added to replace water lost due toevaporation. During this time FTIR spectroscopy indicated that partialconversion of the amorphous calcium carbonate had occurred. Then 16.12grams of overbased magnesium sulfonate A was added. This represents a 3hour and 40 minute magnesium sulfonate delayed addition method relativeto the first addition of water. It also represents a facilitating aciddelay since there was a facilitating acid temperature adjustment delayand several holding delays between the facilitating acid temperatureadjustment delay period and the addition of the magnesium sulfonate (thenext added ingredient that is reactive with the facilitating acid).

Once the overbased magnesium sulfonate was added, FTIR spectroscopyindicated that the conversion of the amorphous calcium carbonate tocrystalline calcium carbonate was completed within 30 minutes. Then11.02 grams of food grade purity calcium hydroxide having a meanparticle size below 5 microns was added and allowed to mix in for 15minutes. Then 1.54 grams of glacial acetic acid and 31.30 grams of12-hydroxystearic acid were added. These two complexing acids wereallowed to react for 30 minutes. During that time another 46.92 grams ofthe same paraffinic base oil was added as the grease continued tothicken. Then 16.00 grams of boric acid mixed in 50 ml of hot water wasadded and allowed to mix in for 15 minutes. Then 17.50 grams of a 75%solution of phosphoric acid in water were slowly added and allowed tomix in and react. The grease was then heated to 340 F. The greaseretained all its grease consistency during the entire heating process.The heating mantle was removed from the mixer and the grease was allowedto cool while continuing to be mixed. When the grease had cooled tobelow 300 F, 40.06 grams of food grade anhydrous calcium sulfate havinga mean particle size below 5 microns were added. When the grease wascooled to 250 F, 2.21 grams of an aryl amine antioxidant were added.Once the grease was cooled to 170 F, four more additions of the sameparaffinic base oil totaling 131.86 grams were added. After additionalmixing, the grease was removed from the mixer and given three passesthrough a three-roll mill to achieve a final smooth homogenous texture.The grease had a worked 60 stroke penetration of 283. The percentoverbased oil-soluble calcium sulfonate in the final grease was 27.36%.The dropping point was >650 F.

Although the examples provided herein fall primarily in the NLGI No. 1,No. 2, or No. 3 grade, with No. 2 grade being the most preferred, itshould be further understood that the scope of this present inventionincludes all NLGI consistency grades harder and softer than a No. 2grade. However, for such greases according to the present invention thatare not NLGI No. 2 grade, their properties should be consistent withwhat would have been obtained if more or less base oil had been used soas to provide a No. 2 grade product, as will be understood by those ofordinary skill in the art.

While this invention deals primarily with greases made in open vessels,and the examples are all in open vessels, the complex calcium magnesiumsulfonate grease compositions and methods may also be used in closedvessels where heating under pressure is accomplished. The use of suchpressurized vessels may result in even better thickener yields thanthose described in the examples herein. For the purposes of thisinvention an open vessel is any vessel with or without a top cover orhatch as long as any such top cover or hatch is not vapor-tight so thatsignificant pressure cannot be generated during heating. Using such anopen vessel with the top cover or hatch closed during the conversionprocess will help to retain the necessary level of water as a convertingagent while generally allowing a conversion temperature at or even abovethe boiling point of water. Such higher conversion temperatures canresult in further thickener yield improvements for both simple andcomplex calcium sulfonate greases, as will be understood by those withordinary skill in the art.

As used herein: (1) quantities of dispersed calcium carbonate (oramorphous calcium carbonate) or residual calcium oxide or calciumhydroxide contained in the overbased calcium sulfonate are by weight ofthe overbased calcium sulfonate; (2) some ingredients are added in twoor more separate portions and each portion may be described as apercentage of the total amount for that ingredient or a percentage offinal grease by weight; and (3) all other amounts (including totalamounts) of ingredients identified by percentages or parts are theamounts added as an ingredient by weight of the final grease product,even though the particular ingredient (such as water, orcalcium-containing bases or alkali metal hydroxides that react withother ingredients) may not be present in the final grease or may not bepresent in the final grease in the quantity identified for addition asan ingredient. As used herein “added calcium carbonate” meanscrystalline calcium carbonate that is added as a separate ingredient inaddition to the amount of dispersed calcium carbonate contained in theoverbased calcium sulfonate. As used herein “added calcium hydroxide”and “added calcium oxide” means calcium hydroxide and calcium oxide,respectively, which are added as a separate ingredient in addition tothe amount of residual calcium hydroxide and/or calcium oxide that maybe contained in the overbased calcium sulfonate. As used herein todescribe the invention (as opposed to how the term is used in some priorart references), calcium hydroxyapatite means (1) the compound havingthe formula Ca₅(PO₄)₃OH or (2) a mathematically equivalent formula (a)having a melting point of around 1100 C or (b) specifically excludingmixtures of tricalcium phosphate and calcium hydroxide by suchequivalent formula.

As used herein, the term “thickener yield” as it applies to the subjectinvention shall be the conventional meaning, namely, the concentrationof the highly overbased oil-soluble calcium sulfonate required toprovide a grease with a specific desired consistency as measured by thestandard penetration tests ASTM D217 or D1403 commonly used inlubricating grease manufacturing. In like manner, as used herein the“dropping point” of a grease shall refer to the value obtained by usingthe standard dropping point test ASTM D2265 as commonly used inlubricating grease manufacturing. Four Ball EP tests as described hereinshall refer to ASTM D2596. Four Ball Wear tests as described hereinshall refer to ASTM D2266. Cone Oil Separation tests as described hereinshall refer to ASTM D6184. Roll Stability tests as described hereinshall refer to ASTM D1831. Those of ordinary skill in the art willappreciate upon reading this specification, including the examplescontained herein, that modifications and alterations to the compositionand methodology for making the composition may be made within the scopeof the invention and it is intended that the scope of the inventiondisclosed herein be limited only by the broadest interpretation of theappended claims to which the inventor is legally entitled.

I claim:
 1. A method of making a sulfonate-based grease comprising:adding and mixing an amount of overbased calcium sulfonate containingamorphous calcium carbonate dispersed therein, an amount of overbasedmagnesium sulfonate, an optional amount of base oil, and water to form apre-conversion mixture; converting the pre-conversion mixture to aconverted mixture by heating until conversion of the amorphous calciumcarbonate to crystalline calcium carbonate has occurred; and wherein noconventional non-aqueous converting agents are added to thepre-conversion mixture.
 2. The method of claim 1 wherein the amount ofoverbased calcium sulfonate is 10-45% and the amount of overbasedmagnesium sulfonate is 0.1-30%.
 3. The method of claim 1 wherein theamount of overbased calcium sulfonate is 10-36% and the amount ofoverbased magnesium sulfonate is 1-24%.
 4. The method of claim 1 whereina first portion of the magnesium sulfonate is added to thepre-conversion mixture and a second portion of the magnesium sulfonateis added to the converted mixture.
 5. The method of claim 4 wherein0.25-95% of the total amount of magnesium sulfonate is added as thefirst portion.
 6. The method of claim 4 wherein 1-75% of the totalamount of magnesium sulfonate is added as the first portion.
 7. Themethod of claim 4 wherein the first and second portions of magnesiumsulfonate combined are 0.2-30% by weight of the final grease and thefirst portion of magnesium sulfonate is 0.1-20% by weight of the finalgrease.
 8. The method of claim 4 wherein the first and second portionsof magnesium sulfonate combined are 0.1-30% by weight of the finalgrease and the first portion of magnesium sulfonate is 0.5-15% by weightof the final grease.
 9. The method of claim 4 wherein the convertedmixture is heated to a temperature in excess of 300 F and then cooled toa temperature below 250 F and wherein the second portion of magnesiumsulfonate is added after the converted mixture is cooled to atemperature below 250 F.
 10. The method of claim 1 further comprisingadding and mixing one or more calcium containing bases with thepre-conversion mixture, the converted mixture, or both; adding andmixing one or more acids with the pre-conversion mixture, the convertedmixture, or both; wherein there is one or more magnesium sulfonate delayperiods between the addition of water, one of the calcium containingbases, one of the acids, or any portion thereof and the addition of atleast a portion of the overbased magnesium sulfonate.
 11. The method ofclaim 10 wherein at least one of the magnesium sulfonate delay periodsis a holding delay period wherein a mixture comprising water, one ormore of the calcium containing bases, one or more of the acids, or anyportion thereof is maintained at a temperature or within a range oftemperatures for a period of time prior to adding at least a portion ofthe magnesium sulfonate; or wherein at least one of the magnesiumsulfonate delay periods is a temperature adjustment delay period whereina mixture comprising water, one or more of the calcium containing bases,one or more of the acids, or any portion thereof is heated or cooledprior to adding at least a portion of the magnesium sulfonate.
 12. Themethod of claim 10 wherein one of the acids is a facilitating acid addedto the pre-conversion mixture and there is at least one magnesiumsulfonate delay period between the addition of the facilitating acid andat least a portion of the magnesium sulfonate.
 13. The method of claim10 wherein a first portion of the magnesium sulfonate is added to thepre-conversion mixture and a second portion of the magnesium sulfonateis added to the converted mixture; and wherein there is a magnesiumsulfonate delay period prior to the addition of the first portion of themagnesium sulfonate, the second portion of the magnesium sulfonate, orboth.
 14. The method of claim 10 wherein the calcium containing basesare calcium hydroxyapatite, added calcium carbonate, added calciumhydroxide, added calcium oxide or a combination thereof.
 15. The methodof claim 10 further comprising adding and mixing an alkali metalhydroxide with the pre-conversion mixture, the converted mixture, orboth.
 16. The method of claim 1 further comprising adding calciumhydroxyapatite, added calcium carbonate, added calcium hydroxide, addedcalcium oxide or a combination thereof to the pre-conversion mixture,the converted mixture, or both.
 17. The method of claim 16 wherein thetotal amount of calcium hydroxyapatite, added calcium carbonate, addedcalcium hydroxide, added calcium oxide or a combination thereof added is2.7-41.2%.
 18. The method of claim 1 further comprising adding andmixing one or more complexing acids in a total amount of 1.25-18%. 19.The method of claim 1 wherein the overbased calcium sulfonate is a poorquality overbased calcium sulfonate.
 20. A sulfonate-based greasecomposition comprising the following ingredients: overbased calciumsulfonate, overbased magnesium sulfonate, water, and an optional baseoil; and wherein water is the sole conventional converting agent. 21.The sulfonate-based grease composition according to claim 20 furthercomprising one or more of the following ingredients: one or more calciumcontaining bases, one or more complexing acids, one or more facilitatingacids, or an alkali metal hydroxide.
 22. The sulfonate-based greasecomposition according to claim 21 wherein amount of overbased calciumsulfonate is around 1.5 to 100 times the amount of overbased magnesiumsulfonate.
 23. The sulfonate-based grease composition according to claim20 wherein the amount of overbased calcium sulfonate is 10-45% and theamount of overbased magnesium sulfonate is 0.1-30%.
 24. Thesulfonate-based grease composition according to claim 20 wherein theamount of overbased calcium sulfonate is 10-36% and the amount ofoverbased magnesium sulfonate is 1-24%.
 25. The sulfonate-based greasecomposition according to claim 21 wherein the calcium containing basesare calcium hydroxyapatite, added calcium carbonate, added calciumoxide, added calcium hydroxide, or a combination thereof and wherein thetotal amount of calcium containing bases is 2.7-41.2%.
 26. Thesulfonate-based grease composition according to 25 wherein the amount ofalkali metal hydroxide is 0.005-0.5%.
 27. The sulfonate-based greasecomposition according to 25 wherein the total amount of one or morecomplexing acids is 1.25-18%.
 28. A pre-conversion sulfonate-basedgrease composition comprising the following ingredients: overbasedcalcium sulfonate, overbased magnesium sulfonate, water, and an optionalbase oil; and wherein water is the sole conventional converting agent.29. The pre-conversion sulfonate-based grease composition according toclaim 28 wherein the composition comprises a ratio of overbased calciumsulfonate to overbased magnesium sulfonate on a weight basis of around100:1 to 60:40.
 30. The pre-conversion sulfonate-based greasecomposition according to claim 28 the composition comprises a ratio ofoverbased calcium sulfonate to overbased magnesium sulfonate on a weightbasis of around 90:10 to 70:30.
 31. The method of claim 1 furthercomprising adding and mixing a facilitating acid with the pre-conversionmixture and wherein there is one or more facilitating acid delay periodsbetween the addition of the facilitating acid and at least a portion ofany subsequently added ingredient; and wherein the one or morefacilitating acid delay periods comprise: a facilitating acid holdingdelay period where the initial mixture is held at a temperature or rangeof temperatures for a period of time of 20 minutes or more betweenadding the facilitating acid and the subsequent addition of at least aportion of another ingredient, or a facilitating acid temperatureadjustment delay period where the initial mixture is heated or cooled toa temperature or range of temperatures after adding the facilitatingacid and prior to the subsequent addition of at least a portion ofanother ingredient, or a combination thereof.
 32. The method of claim 31wherein there is at least one facilitating acid temperature adjustmentdelay period where the pre-conversion mixture is heated to a temperaturerange of 190-200 F after adding the facilitating acid and prior to thesubsequent addition of at least a portion of another ingredient.
 33. Themethod of claim 31 wherein there is at least one facilitating acidholding delay period where the pre-conversion mixture is held at atemperature range of 190-200 F for around 20-30 minutes prior to thesubsequent addition of at least a portion of another ingredient.
 34. Themethod of claim 31 wherein the facilitating acid holding delay period is20 minutes or more if the next added ingredient is reactive with thefacilitating acid.
 35. The method of claim 31 wherein the facilitatingacid holding delay period is 30 minutes or more.